EP4130147A1 - Zusammensetzung, film und optischer sensor - Google Patents

Zusammensetzung, film und optischer sensor Download PDF

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Publication number
EP4130147A1
EP4130147A1 EP21779485.8A EP21779485A EP4130147A1 EP 4130147 A1 EP4130147 A1 EP 4130147A1 EP 21779485 A EP21779485 A EP 21779485A EP 4130147 A1 EP4130147 A1 EP 4130147A1
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EP
European Patent Office
Prior art keywords
group
resin
constitutional unit
formula
film
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EP21779485.8A
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English (en)
French (fr)
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EP4130147A4 (de
Inventor
Kyohei Arayama
Shunsuke Kitajima
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Fujifilm Corp
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Fujifilm Corp
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Publication of EP4130147A1 publication Critical patent/EP4130147A1/de
Publication of EP4130147A4 publication Critical patent/EP4130147A4/de
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/20—Aqueous medium with the aid of macromolecular dispersing agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/061—Polyesters; Polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/062—Polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
    • C08G63/6852—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from hydroxy carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • C08G63/912—Polymers modified by chemical after-treatment derived from hydroxycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/67—Particle size smaller than 100 nm
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/68—Particle size between 100-1000 nm
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/222—Magnesia, i.e. magnesium oxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2244—Oxides; Hydroxides of metals of zirconium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3009—Sulfides
    • C08K2003/3036—Sulfides of zinc
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3045—Sulfates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/201—Filters in the form of arrays

Definitions

  • the present invention relates to a composition, a film, and an optical sensor.
  • Titanium oxide is particles having a high refractive index. Attempts to use such particles having a high refractive index for a light scattering film or the like have been studied.
  • JP2016-161859A discloses an invention of a light scattering sheet including a plurality of polymers having different refractive indexes from each other and including a light scattering layer having a co-continuous phase structure in at least a part of a region, in which an incidence ray is isotropically transmitted and scattered, a scattering angle showing the maximal value of intensity of scattered light is 2° to 40°, and a total light transmittance is 70% to 100%. It is said that any continuous phase forming the co-continuous phase structure may include high refraction fine particles.
  • WO2017/150112A discloses a dispersion composition containing a colorant and a resin, in which the resin contains a structural unit A having a polymer chain and a structural unit B having an acidic group, the polymer chain contains two or more kinds of structural units GF, and the structural unit GF is selected from the group consisting of a structural unit composed of an oxyalkylene group and a structural unit composed of an oxyalkylene carbonyl group.
  • An object of the present invention is to provide a composition with which a film having excellent adhesiveness and light scattering properties can be formed, a film consisting of the composition or a film having excellent adhesiveness and light scattering properties, and an optical sensor including the film.
  • compositions which has excellent storage stability and with which a film having excellent adhesiveness and light scattering properties can be formed, a film consisting of the composition or a film having excellent adhesiveness and light scattering properties, and an optical sensor including the film.
  • a group (atomic group) denotes not only a group (atomic group) having no substituent but also a group (atomic group) having a substituent.
  • alkyl group denotes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • (meth)acrylate represents acrylate or methacrylate
  • (meth)acryl represents acryl and methacryl
  • (meth)allyl represents allyl and methallyl
  • (meth)acryloyl represents acryloyl and methacryloyl.
  • Me represents a methyl group
  • Et represents an ethyl group
  • Pr represents a propyl group
  • Bu represents a butyl group
  • Ph represents a phenyl group.
  • exposure denotes not only exposure using light but also drawing using a corpuscular beam such as an electron beam or an ion beam.
  • a corpuscular beam such as an electron beam or an ion beam.
  • the light used for exposure include an actinic ray or radiation, for example, a bright light spectrum of a mercury lamp, a far ultraviolet ray represented by excimer laser, an extreme ultraviolet ray (EUV ray), an X-ray, or an electron beam.
  • a weight-average molecular weight and a number-average molecular weight are defined as values in terms of polystyrene measured by gel permeation chromatography (GPC).
  • the weight-average molecular weight (Mw) and the number-average molecular weight (Mn) can be obtained, for example, by using HLC-8220GPC (manufactured by Tosoh Corporation), using a column in which TOSOH TSK gel Super HZM-H, TOSOH TSK gel Super HZ4000, and TOSOH TSK gel Super HZ2000 are linked to each other, and using tetrahydrofuran as a developing solvent.
  • a value of refractive index is a value of refractive index with refractive index to light at a wavelength of 589 nm at 23°C, unless otherwise specified.
  • a composition according to an embodiment of the present invention includes white particles having a refractive index of 2.0 or more and an average primary particle diameter of 200 nm or less, a film-forming component including at least one selected from the group consisting of a resin and a polymerizable monomer, and a solvent, in which the film-forming component includes two or more kinds of resins, or includes one or more kinds of resins and one or more kinds of polymerizable monomers, at least one of the resin is a resin A which contains a constitutional unit A having a formula weight of 1,000 or more and including a constitutional unit GF and a constitutional unit B having an acidic group, and satisfies at least one of the following requirement 1 or the following requirement 2, and the constitutional unit GF is a constitutional unit selected from the group consisting of a constitutional unit represented by Formula (1-1) and a constitutional unit represented by Formula (1-2).
  • the constitutional unit A includes a molecular chain containing two or more kinds of the constitutional units GF.
  • the resin A contains two or more kinds of the constitutional units A having different structures of the constitutional unit GF.
  • R A represents a divalent organic group and R B represents a divalent organic group.
  • composition according to the embodiment of the present invention includes, as a film-forming component, two or more kinds of resins or one or more kinds of resins and one or more kinds of polymerizable monomers, in which at least one of the resins is the resin A having a specific structure.
  • a position of the white particles may be biased in the film, and it is considered that the first phase which is a region having a large refractive index and the second phase which is a region having a small refractive index coexist in the film. Since light is scattered between these two phases, it is presumed that the film obtained by the composition according to the embodiment of the present invention has excellent light scattering properties.
  • the resin A contains the constitutional unit A including a constitutional unit GF and the constitutional unit B having an acidic group, and satisfies the above-described requirement 1 or requirement 2.
  • the resin A contains the constitutional unit GF, it is considered that a film having excellent light scattering properties on a long wavelength side (for example, a wavelength of 940 nm or more) can be obtained.
  • a film having excellent light scattering properties on a long wavelength side for example, a wavelength of 940 nm or more
  • crystallinity and phase separability of the resin A are improved, and it is presumed that, regardless of whether the resin A is included in the first phase or the second phase, the size of the above-described first phase is large to some extent.
  • the resin A satisfies at least one of the above-described requirement 1 or requirement 2, it is considered that a film having excellent light scattering properties on a short wavelength side (for example, a wavelength of 450 nm or less) can be obtained.
  • the crystallinity and phase separability of the resin A are not too large, and it is presumed that, regardless of whether the resin A is included in the first phase or the second phase, the size of the above-described first phase is small to some extent.
  • the size of the first phase can be set to an appropriate size, it is presumed that the light scattering properties are excellent.
  • the light scattering properties are excellent particularly in a wide range of wavelengths (for example, 400 nm to 1,000 nm).
  • the resin A contains the constitutional unit B having an acidic group.
  • the particles having a high refractive index (hereinafter, also referred to as high-refractive particles) generally tend to have a large specific gravity.
  • the particles having a large specific gravity are contained and used in a composition including a solvent, the particles may settle during storage of the composition. Therefore, with a known composition in the related art, it may be difficult to achieve both storage stability and light scattering properties of the obtained film at a high level.
  • composition according to the embodiment of the present invention has good storage stability.
  • the composition according to the embodiment of the present invention includes white particles having a refractive index of 2.0 or more and an average primary particle diameter of 200 nm or less.
  • white particles having a refractive index of 2.0 or more generally have a large specific gravity, but in the composition according to the embodiment of the present invention, since the white particles having a relatively small particle diameter with an average primary particle diameter of 200 nm or less are used as the particles having a refractive index of 2.0 or more, sedimentation of the particles in the composition including a solvent can be suppressed, and as a result, it is presumed that the storage stability of the composition is good.
  • the resin A satisfies at least one of the above-described requirement 1 or requirement 2, it is considered that generation of foreign matter in the film is likely to be suppressed even after the film formed of the composition is formed and then stored in a state of the film (for example, storage for 72 hours).
  • the fact that the generation of foreign matter in the film after storage is suppressed as described above is also referred to as that "generation of foreign matter over time is suppressed". Since the resin A satisfies at least one of the above-described requirement 1 or requirement 2, it is presumed that the crystallinity of the resin A itself is lowered and crystallization in the film is suppressed.
  • the light scattering sheet of the invention disclosed in JP2016-161859A is said to have a total light transmittance of 70% to 100%, the light scattering sheet of the invention disclosed in JP2016-161859A is not a member which appropriately blocks visible light, but rather has high visible light transmittance.
  • composition according to the embodiment of the present invention in a case where the composition is heated to form a film having a thickness of 4 ⁇ m, it is preferable that a phase-separated structure between a first phase including the particles and a second phase with a lower content of the particles than the first phase is formed in the film.
  • the light scattering properties can be improved, and angle dependence of the scattered light can be reduced.
  • a base material of the first phase and the second phase is the film-forming component or a cured substance derived from the film-forming component.
  • the above-described first phase is a phase in which the above-described particles are present in the film-forming component or the cured substance derived from the film-forming component.
  • the second phase has a lower content of the above-described particles than the first phase, and the second phase may not substantially include the above-described particles. For the reason that it is easy to obtain more excellent light scattering properties, it is preferable that the second phase does not substantially include the above-described particles.
  • the formation of the phase-separated structure between the first phase and the second phase in the film can be observed using a scanning electron microscope (SEM), a transmission electron microscope (TEM), or an optical microscope.
  • SEM scanning electron microscope
  • TEM transmission electron microscope
  • the composition is applied to a support such as a glass substrate and heated at 200°C for 5 minutes to form a film having a thickness of 4 ⁇ m, and then a cross section of the obtained film in a thickness direction is observed using a scanning electron microscope (SEM), a transmission electron microscope (TEM), or an optical microscope.
  • SEM scanning electron microscope
  • TEM transmission electron microscope
  • the composition includes a polymerizable compound and a photopolymerization initiator as a film-forming component
  • exposure for curing the polymerizable compound may be performed before the heating.
  • the above-described phase-separated structure can be formed by appropriately changing the types of resins (for example, the resin A and a resin other than the resin A) and polymerizable monomers used as the film-forming component included in the composition.
  • resins for example, the resin A and a resin other than the resin A
  • polymerizable monomers used as the film-forming component included in the composition.
  • Examples of one aspect thereof include a method of using, as the film-forming component, a first resin and a second resin having low compatibility with the first resin.
  • a phase-separated structure between a phase including the first resin as a main component and a phase including the second resin as a main component can be formed during film formation.
  • one of the first resin or the second resin is a resin as a particle dispersant and the other is a binder resin
  • many particles can be unevenly distributed in the phase including the resin as a dispersant as a main component.
  • examples of another aspect thereof include a method of using, as the film-forming component, a first resin and a polymerizable monomer having low compatibility with the first resin.
  • a phase-separated structure between a phase including the first resin as a main component and a phase including a cured substance derived from the polymerizable monomer as a main component can be formed during film formation.
  • examples of still another aspect thereof include a method in which the type of the resin or the polymerizable monomer used in the film-forming component is appropriately changed, and the film-forming component is spinodally decomposed during film formation to form a phase-separated structure between the first phase and the second phase.
  • the phase-separated structure in the above-described film preferably has a phase interface isotropically present in the film, and for example, more preferably a sea-island structure or a co-continuous phase structure.
  • a phase interface isotropically present in the film and for example, more preferably a sea-island structure or a co-continuous phase structure.
  • the sea-island structure is a structure formed by a sea region which is a continuous region and an island region which is a discontinuous region.
  • the second phase may form the sea and the first phase may form the island, or the first phase may form the sea and the second phase may form the island.
  • the co-continuous phase structure is a network structure in which the first phase and the second phase each form a continuous phase structure intrusive to each other.
  • the maximum value of the transmittance of the above-described film to light at 400 to 1,000 nm is preferably 80% or less, more preferably 70% or less, still more preferably 60% or less, and particularly preferably 50% or less.
  • the lower limit of the above-described maximum value of the light transmittance is preferably 1% or more, more preferably 5% or more, and still more preferably 10% or more.
  • the maximum value of the transmittance of the film to light having a wavelength in a range of 400 to 700 nm is preferably 80% or less, more preferably 70% or less, still more preferably 60% or less, and particularly preferably 50% or less.
  • the lower limit of the above-described maximum value of the light transmittance is preferably 1% or more, more preferably 5% or more, and still more preferably 10% or more.
  • Heating conditions for confirming the above-described phase-separated structure or heating conditions for measuring the maximum value of the above-described transmittance may be appropriately set according to components included in the composition, and preferred examples thereof include heating at 200°C for 5 minutes.
  • the average value of a difference in refractive index between the phases in the above-described film is preferably 0.1 or more, more preferably 0.2 or more, still more preferably 0.3 or more, and particularly preferably 0.4 or more.
  • the haze of the above-described film based on JIS K 7136 is preferably 30% to 100%.
  • the upper limit is preferably 99% or less, more preferably 95% or less, and still more preferably 90% or less.
  • the lower limit is preferably 35% or more, more preferably 40% or more, and still more preferably 50% or more.
  • the formation of the film having such spectral characteristics can be achieved by appropriately adjusting a shape of the phase-separated structure, a refractive index of the particles, an abundance of the particles in the film, a degree of uneven distribution of the particles in the film, and the like.
  • the concentration of solid contents of the composition according to the embodiment of the present invention is preferably 5 to 80 mass%.
  • the upper limit is preferably 75 mass% or less and more preferably 70 mass% or less.
  • the lower limit is preferably 10 mass% or more, more preferably 15 mass% or more, and still more preferably 20 mass% or more.
  • the composition according to the embodiment of the present invention includes white particles (hereinafter, also referred to as particles P1) having a refractive index of 2.0 or more and an average primary particle diameter of 200 nm or less.
  • the average primary particle diameter of the particles P1 is 200 nm or less, and from the viewpoint of storage stability of the composition, is preferably 100 mn or less.
  • the average primary particle diameter of the particles P1 is preferably 5 nm to 100 nm, more preferably 10 nm to 100 nm, still more preferably 20 nm to 100 nm, even more preferably 30 nm to 100 nm, even still more preferably 40 nm to 100 nm, and particularly preferably 50 nm to 100 nm.
  • the average primary particle diameter of particles is a value measured by the following method. That is, the primary particle diameter of the particles can be obtained by observing the particles with a transmission electron microscope (TEM) and observing a portion (primary particle) where the particles do not aggregate. A particle size distribution of the particles can be obtained by photographing a transmission electron micrograph of the primary particles using a transmission electron microscope and measuring a particle size distribution with an image processing device using the micrograph.
  • the average primary particle diameter of the particles refers to the number average particle size calculated from the particle size distribution.
  • an electron microscope H-7000, manufactured by Hitachi, Ltd.
  • a LUZEX AP manufactured by Nireco Corporation
  • the refractive index of the particles P1 is 2.0 or more, preferably 2.2 or more and more preferably 2.4 or more.
  • the upper limit of the refractive index of the particles P1 is not particularly limited, but may be 5 or less or 4 or less.
  • the refractive index of particles is a value measured by the following method.
  • a dispersion liquid is prepared using the particles, a resin (dispersant) having a known refractive index, and propylene glycol monomethyl ether acetate.
  • the prepared dispersion liquid and a resin having a known refractive index are mixed with each other to prepare coating liquids in which the concentrations of the particles is 10 mass%, 20 mass%, 30 mass%, and 40 mass% with respect to the total solid content of the coating liquids.
  • a film having a thickness of 300 nm is formed on a silicon wafer, and the refractive index of the obtained film is measured by ellipsometry (LAMBDA ACE RE-3300, manufactured by SCREEN Holdings Co., Ltd.). Next, the refractive index corresponding to the concentration of the particles is plotted on a graph to derive the refractive index of the particles.
  • the specific gravity of the particles P1 is preferably 1 to 7 g/cm 3 .
  • the upper limit is preferably 6 g/cm 3 or less and more preferably 5 g/cm 3 or less.
  • the lower limit of the specific gravity is not particularly limited, but may be 1.5 g/cm 3 or more or 2 g/cm 3 or more.
  • the specific gravity of particles is a value measured by the following method. First, 50 g of particles are put into a 100 mL volumetric flask. Subsequently, 100 mL of water is weighed using another 100 mL graduated cylinder. Thereafter, first, the weighed water is put into the volumetric flask to the extent that the particles are immersed, and then ultrasonic waves are applied to the volumetric flask to allow the particles and water to blend in. Next, additional water is added thereto until the marked line of the volumetric flask is reached, and the specific gravity is calculated as 50 g/(volume of water remaining in volumetric flask).
  • the particles P1 are white particles.
  • the particles P1 are preferably inorganic particles.
  • examples of the type of the inorganic particles include titanium oxide particles, strontium titanate particles, barium titanate particles, zinc oxide particles, magnesium oxide particles, zirconium oxide particles, aluminum oxide particles, barium sulfate particles, and zinc sulfide particles.
  • the inorganic particles used as the particles P1 are preferably particles having a titanium atom and more preferably titanium oxide particles.
  • the content (purity) of titanium dioxide (TiO 2 ) is preferably 70 mass% or more, more preferably 80 mass% or more, and still more preferably 85 mass% or more.
  • the content of lower titanium oxide represented by Ti n O 2n-1 (n represents a number of 2 to 4), titanium nitride, or the like is preferably 30 mass% or less, more preferably 20 mass% or less, and still more preferably 15 mass% or less.
  • the titanium oxide may be rutile type titanium oxide or anatase type titanium oxide. From the viewpoint of colorability and the temporal stability of the dispersion liquid or the composition, rutile type titanium oxide is preferable. In particular, rutile type titanium oxide has a small change in color difference and excellent colorability even under heating. In addition, the rutile transformation rate of the titanium oxide is preferably 95% or more and more preferably 99% or more.
  • rutile type titanium oxide a well-known titanium oxide can be used.
  • a method of manufacturing rutile type titanium oxide two methods including a sulfuric acid method and a chlorine method are present, and a titanium oxide manufactured using any one of the methods can be suitably used.
  • the sulfuric acid method refers to a manufacturing method including: dissolving ilmenite ore or titanium slug as a raw material in concentrated sulfuric acid to separate iron as iron sulfate; hydrolyzing the separated solution to obtain a precipitate of hydroxide; and calcinating the precipitate at a high temperature to extract rutile type titanium oxide.
  • the chlorine method refers to a manufacturing method including: causing synthetic rutile or natural rutile as a raw material to react with chlorine gas or carbon at a high temperature of approximately 1,000°C to synthesize of titanium tetrachloride; and oxidizing the titanium tetrachloride at a high temperature to extract rutile type titanium oxide. It is preferable that rutile type titanium oxide is obtained using the chlorine method.
  • a value measured using a Brunauer, Emmett, Teller (BET) method is preferably 10 to 400 m 2 /g, more preferably 10 to 200 m 2 /g, still more preferably 10 to 150 m 2 /g, particularly preferably 10 to 40 m 2 /g, and most preferably 10 to 20 m 2 /g.
  • the pH of titanium oxide is preferably 6 to 8.
  • the oil absorption of titanium oxide is preferably 10 to 60 (g/100 g) and more preferably 10 to 40 (g/100 g).
  • the total content of Fe 2 O 3 , Al 2 O 3 , SiO 2 , Nb 2 O 5 , and Na 2 O is preferably 0.1 mass% or less, more preferably 0.05 mass% or less, still more preferably 0.02 mass% or less, and particularly preferably substantially 0 mass%.
  • the shape of the titanium oxide particles is not particularly limited.
  • Examples of the shape of titanium oxide include an isotropic shape (for example, a spherical shape and a polyhedral shape), an anisotropic shape (for example, a needle shape, a rod shape, and a plate shape), and an unstructured shape.
  • the hardness (Mohs hardness) of titanium oxide particles is preferably 5 to 8 and more preferably 7 to 7.5.
  • the inorganic particles such as the titanium oxide particles may be surface-treated with a surface treatment agent such as an organic compound.
  • a surface treatment agent such as an organic compound.
  • the surface treatment agent used for the surface treatment of the titanium oxide include polyol, aluminum oxide, aluminum hydroxide, silica (silicon oxide), water-containing silica, alkanolamine, stearic acid, organosiloxane, zirconium oxide, hydrogen dimethicone, a silane coupling agent, and a titanate coupling agent.
  • a silane coupling agent is preferable.
  • the surface treatment may be performed using one surface treatment agent alone or a combination of two or more surface treatment agents.
  • the inorganic particles such as the titanium oxide particles are covered with a basic metal oxide or a basic metal hydroxide.
  • the basic metal oxide or the basic metal hydroxide include a metal compound including magnesium, zirconium, cerium, strontium, antimony, barium, calcium, or the like.
  • titanium oxide particles titanium oxide particles described in "Titanium Oxide - Physical Properties and Applied Technology, Manabu Kiyono, pp. 13 to 45, June 25, 1991, published by Gihodo Shuppan Co., Ltd.) can also be suitably used.
  • a commercially available product can be preferably used.
  • the commercially available product may be used as it is or may be used after a classification treatment.
  • Examples of the commercially available product of titanium oxide particles include:
  • Examples of a commercially available product of strontium titanate particles include SW-100 (manufactured by Titan Kogyo Ltd.).
  • Examples of a commercially available product of barium sulfate particles include BF-1L (manufactured by Sakai Chemical Industry Co., Ltd.).
  • Examples of a commercially available product of zinc oxide particles include Zincox Super F-1 (manufactured by Hakusui Chemical Co., Ltd.).
  • Examples of a commercially available product of zirconium oxide particles include Z-NX (manufactured by Taiyo Koko Co., Ltd.) and Zirconeo-Cp (manufactured by ITEC Co., Ltd.).
  • the content of the particles P1 in the total solid content of the composition is preferably 5 to 90 mass%.
  • the upper limit is preferably 85 mass%% or less, more preferably 80 mass% or less, and still more preferably 70 mass% or less.
  • the lower limit is preferably 6 mass% or more, more preferably 10 mass% or more, and still more preferably 15 mass% or more.
  • the composition according to the embodiment of the present invention may include only one kind of the particles P1 or two or more kinds of the particles P1. In a case where only one kind of the particles P1 is included, more excellent storage stability is easily obtained. In addition, in a case where two or more kinds of the particles P1 are included, the angle dependence of light scattering can be further reduced. In a case where two or more kinds of the particles P1 are included, the total content thereof is preferably within the above-described range.
  • the composition according to the embodiment of the present invention can contain particles (hereinafter, also referred to as particles P2) having a refractive index of less than 2.0, an average primary particle diameter of 500 nm or more, and a specific gravity smaller than that of the particles P1.
  • particles P2 having a refractive index of less than 2.0, an average primary particle diameter of 500 nm or more, and a specific gravity smaller than that of the particles P1.
  • the composition according to the embodiment of the present invention contains P2 in addition to P1, scattering occurs between the particles P1 and the particles P2, so that light irradiated to the film can be efficiently scattered and transmitted. Therefore, by using such a composition, a film having more excellent light scattering properties can be formed.
  • the average primary particle diameter of the particles P2 is 500 nm or more, preferably 500 nm to 6,000 nm, more preferably 500 nm to 5,000 nm, still more preferably 500 nm or more and less than 3,000 nm, even more preferably 500 nm to 2,500 nm, even still more preferably 500 nm to 2,000 nm, particularly preferably 500 nm to 1,500 nm, and most preferably 500 nm to 1,000 nm.
  • the refractive index of the particles P2 is less than 2.0, preferably 1.9 or less, more preferably 1.8 or less, and particularly preferably 1.7 or less.
  • the lower limit of the refractive index of the particles P2 is not particularly limited, and may be 1.0 or more or 1.1 or more.
  • the difference between the refractive index of the particles P1 and the refractive index of the particles P2 is preferably 0.5 or more, more preferably 0.7 or more, and still more preferably 0.9 or more.
  • the mass average value of the refractive indexes of two or more kinds of the particles P1 is used as the value of the refractive index of the particles P1.
  • the composition according to the embodiment of the present invention includes two or more kinds of the particles P2.
  • the specific gravity of the particles P2 is preferably 2.5 g/cm 3 or less, more preferably 2.4 g/cm 3 or less, still more preferably 2.2 g/cm 3 or less, and particularly preferably 2.0 g/cm 3 or less.
  • the lower limit of the specific gravity of the particles P2 is not particularly limited, but may be 0.5 g/cm 3 or more or 0.9 g/cm 3 or more.
  • the particles P2 are preferably transparent or white particles.
  • the particles P2 include inorganic particles and resin particles.
  • the type of the inorganic particles include silica particles, hollow titanium oxide particles, and hollow zirconia particles. Among these, silica particles are preferable.
  • Examples of a commercially available product of the inorganic particles include Sylysia series manufactured by FUJI SILYSIA CHEMICAL LTD. (for example, Sylysia 310P and the like) and Seahostar series manufactured by NIPPON SHOKUBAI CO., LTD. (for example, Seahostar KE-S250).
  • the resin particles include particles consisting of a synthetic resin such as a (meth)acrylic resin, a styrene resin, a polyamide resin, a polyimide resin, a polyolefin resin, a polyurethane resin, a polyurea resin, a polyester resin, a melanin resin, and a silicone resin, and particles consisting of a natural polymer such as chitin, chitosan, cellulose, crosslinked starch, and crosslinked cellulose.
  • the synthetic resin particles are preferably used because they have advantages such as easy control of particle size.
  • fine particles can be formed according to a crushing method, but a method of producing resin particles according to an emulsification and suspension polymerization method is preferable from the viewpoint of case of controlling the particle diameter, and precision.
  • the method of producing the resin particles is described in detail in " Ultrafine Particles and Materials” edited by Materials Science Society of Japan, published by SHOKABO Co., Ltd., published in 1993 , " Manufacturing & Application of Microspheres & Powders” supervised by Haruma Kawaguchi, published by CMC Publishing Co., Ltd., published in 2005 , and the like.
  • the resin particles are also available as commercially available products, and examples thereof include MX-40T, MX-80H3wT, MX-150, MX-180TA, MX-300, MX-500, MX-1000, MX-1500H, MR-2HG, MR-7HG, MR-10HG, MR-3GSN, MR-5GSN, MR-7G, MR-10G, MR-5C, and MR-7GC (all manufactured by Soken Chemical & Engineering Co., Ltd., acrylic resin particles); SX-130H, SX-350H, and SX-500H (all manufactured by Soken Chemical & Engineering Co., Ltd., styrene resin particles); MBX-5, MBX-8, MBX-12, MBX-15, MBX-20, MB20X-5, MB30X-5, MB30X-8, MB30X-20, SBX-6, SBX-8, SBX-12, and SBX-17 (all manufactured by Sekisui Plastics Co., Ltd.,
  • the particles P2 are also preferably hollow particles.
  • the hollow particles refer to particles having voids in which no material constituting the particles exists inside a surface of the particles.
  • the size, shape, and number of voids are not particularly limited.
  • the hollow particles may have an outer shell structure have a void in the central portion, or a structure in which a plurality of fine voids are dispersed inside the particles.
  • the void ratio of the hollow particles is preferably 1% to 90%.
  • the lower limit of the void ratio is preferably 5% or more and more preferably 10% or more.
  • the upper limit of the void ratio is preferably 85% or less and more preferably 80% or less.
  • the void ratio of the hollow particles refers to a proportion of the volume occupied by the voids to the total volume of the hollow particles.
  • the void ratio of the hollow particles can be obtained by observing hollow particles using a transmission electron microscope, measuring an outer diameter and a void diameter, and calculating "the proportion of the volume occupied by the void to the total volume" according to the following expression. Void diameter 3 / Outer diameter 3 ⁇ 100 %
  • More specific examples thereof include a method in which 100 hollow particles observed by a transmission electron microscope are optionally selected, equivalent circle diameters of an outer and a void of each of these hollow particles are measured to obtain the outer diameter and the void diameter, and a void ratio is calculated according to the above expression and an average value thereof is determined as the void ratio.
  • the void ratio can be also be known from the measurement of the refractive index of the particles.
  • the shape of the hollow particles is preferably spherical, but may be a shape other than the spherical shape, such as an amorphous shape.
  • the hollow particles may be hollow particles formed of an inorganic material (hereinafter, also referred to as hollow inorganic particles), or may be hollow particles formed of a resin material (hereinafter, also referred to as hollow resin particles).
  • an inorganic material hereinafter, also referred to as hollow inorganic particles
  • a resin material hereinafter, also referred to as hollow resin particles
  • Examples of the material constituting the hollow resin particles include a (meth)acrylic resin, a styrene resin, a polyamide resin, a polyimide resin, a polyolefin resin, a polyurethane resin, a polyurea resin, a polyester resin, a silicone resin, and a melanin resin.
  • a (meth)acrylic resin or a styrene resin is preferable, and a (meth)acrylic resin is more preferable.
  • Examples of a method for manufacturing the hollow resin particles include a method of containing a forming agent in the resin particles and foaming the forming agent, a method of encapsulating a volatile substance in the resin particles and gasifying the volatile substance to be expanded, a method of melting the resin particles and injecting a gas such as air into the resin particles, and a method (hereinafter, also referred to as a solvent removal method) in which a polymerizable monomer and a non-polymerizable solvent are mixed and polymerized to obtain resin particles encompassing the solvent, and the solvent is removed.
  • a solvent removal method in which a polymerizable monomer and a non-polymerizable solvent are mixed and polymerized to obtain resin particles encompassing the solvent, and the solvent is removed.
  • the hollow inorganic particles are preferably hollow silica particles. That is, the hollow inorganic particles are preferably silica particles having a void in the central portion. Specific examples of the hollow silica particles include hollow particles described in JP2013-237593A , WO2007/060884A , and the like.
  • the content of the particles P2 in the total solid content of the composition is preferably 1 to 90 mass%.
  • the upper limit is preferably 80 mass%% or less, more preferably 70 mass% or less, and still more preferably 60 mass% or less.
  • the lower limit is preferably 2 mass% or more, more preferably 5 mass% or more, and still more preferably 10 mass% or more.
  • the composition according to the embodiment of the present invention may include only one kind of the particles P2 or two or more kinds of the particles P2. In a case where only one kind of the particles P2 is included, more excellent storage stability is easily obtained. In addition, in a case where two or more kinds of the particles P2 are included, the angle dependence of light scattering can be further reduced. In a case where two or more kinds of the particles P2 are included, the total content thereof is preferably within the above-described range.
  • the total content of the particles P1 and the particles P2 in the total solid content of the composition is preferably 30 mass% or more, more preferably 35 mass% or more, and still more preferably 40 mass% or more.
  • the upper limit is preferably 90 mass%% or less, more preferably 80 mass% or less, and still more preferably 70 mass% or less.
  • the particles P1 is 20 to 500 parts by mass with respect to 100 parts by mass of the particles P2.
  • the upper limit is preferably 450 parts by mass or less, more preferably 400 parts by mass or less, and still more preferably 300 parts by mass or less.
  • the lower limit is preferably 25 parts by mass or more, more preferably 30 parts by mass or more, and still more preferably 35 parts by mass or more.
  • a content of the white particles (for example, total content of the above-described particles P1 and the above-described particles P2 as the white particles) in the composition according to the embodiment of the present invention is preferably 80 mass% or more, more preferably 90 mass% or more, still more preferably 95 mass% or more, particularly preferably 98 mass% or more, and most preferably 99 mass% or more with respect to the total mass of all particles included in the composition.
  • the upper limit of the above-described content thereof is not particularly limited, and may be 100 mass%.
  • the composition according to the embodiment of the present invention includes a film-forming component including at least one selected from a resin or a polymerizable monomer.
  • the film-forming component used in the present invention includes two or more kinds of resins, or includes one or more kinds of resins and one or more kinds of polymerizable monomers.
  • composition according to the embodiment of the present invention includes the resin A as the film-forming component.
  • the resin A contains a constitutional unit A having a formula weight of 1,000 or more and including a constitutional unit GF and a constitutional unit B having an acidic group, and satisfies at least one of the following requirement 1 or the following requirement 2, and the constitutional unit GF is a constitutional unit selected from the group consisting of a constitutional unit represented by Formula (1-1) and a constitutional unit represented by Formula (1-2).
  • the constitutional unit A includes a molecular chain containing two or more kinds of the constitutional units GF.
  • the resin A contains two or more kinds of the constitutional units A having different structures of the constitutional unit GF.
  • the resin A is blended in, for example, an application for dispersing particles in a composition or an application as a binder.
  • a resin which is used for dispersing particles is also referred to as a dispersant.
  • such applications of the resin are only exemplary, and the resin can also be used for other purposes in addition to such applications.
  • the resin A is preferably blended for the purpose of a binder.
  • the resin A satisfies at least one of the requirement 1 or the requirement 2.
  • the requirement 1 means that the constitutional unit A includes a molecular chain containing at least two constitutional units GF. It is sufficient that the type of the constitutional unit GF in the constitutional unit A is 2 or more, and for example, the type thereof can be 2 to 10, preferably 2 to 4.
  • the requirement 2 means that the resin A has one constitutional unit A and another constitutional unit A, and a constitutional unit GF included in one constitutional unit A and a constitutional unit GF included in another constitutional unit A are different from each other.
  • the resin A may satisfy both the requirement 1 and the requirement 2. That is, the resin A may have one constitutional unit A and another constitutional unit A, in which a constitutional unit GF included in one constitutional unit A and a constitutional unit GF included in another constitutional unit A are different from each other, and at least one of one constitutional unit A or another constitutional unit A may include a molecular chain containing the constitutional unit GF.
  • the resin A satisfies at least the requirement 1.
  • the constitutional unit A is a constitutional unit A having a formula weight of 1,000 or more, and includes a constitutional unit GF.
  • the formula weight of the constitutional unit A is not particularly limited, but is preferably 1,000 to 100,000, more preferably 1,500 to 50,000, still more preferably 2,000 to 50,000, and particularly preferably 2,500 to 30,000.
  • the constitutional unit A includes a molecular chain containing two or more kinds of the constitutional units GF.
  • the two or more kinds of the constitutional units GF are intended to be two or more kinds of constitutional units having different structures from each other. More specific examples of an aspect of the two or more kinds of the constitutional units GF include a case where different types of constitutional units are included in the constitutional unit A, such as a combination of a constitutional unit represented by Formula (1-1) and a constitutional unit represented by Formula (1-2). In addition, examples thereof also include an aspect in which the molecular chain includes two or more kinds of constitutional units represented by Formula (1-1), which have different structures of R A .
  • a proportion of a molar amount of the most constitutional unit among constitutional units corresponding to the constitutional unit GF to the total molar amount of the constitutional units corresponding to the constitutional unit GF included in the constitutional unit A is preferably 20% to 98%, more preferably 30% to 95%, and still more preferably 40% to 90%.
  • a proportion of a molar amount of constitutional units most included in the constitutional unit A, which correspond to the constitutional unit GF, to the total molar amount of the constitutional units corresponding to the constitutional unit GF included in the constitutional unit A is preferably 50% to 90%, more preferably 60% to 90%, and still more preferably 70% to 85%.
  • the resin A In a case where the resin A satisfies the requirement 2, the resin A has one constitutional unit A and another constitutional unit A, and a constitutional unit GF included in one constitutional unit A and a constitutional unit GF included in another constitutional unit A are different from each other.
  • a proportion of a molar amount of the most constitutional unit among constitutional units corresponding to the constitutional unit GF to the total molar amount of the constitutional units corresponding to the constitutional unit GF included in the resin A is preferably 20% to 98%, more preferably 30% to 95%, and still more preferably 40% to 90%.
  • a proportion of a molar amount of constitutional units most included in the constitutional unit A, which correspond to the constitutional unit GF, to the total molar amount of the constitutional units corresponding to the constitutional unit GF included in the constitutional unit A is preferably 50% to 90%, more preferably 60% to 90%, and still more preferably 70% to 85%.
  • the constitutional unit A preferably includes a polymer structure.
  • the polymer structure included in the constitutional unit A may be a polymer in which the formula weight of the constitutional unit A is within the above-described range, and examples thereof include a molecular chain having a molecular weight (in a case of having a molecular weight distribution, a weight-average molecular weight) of 1,000 or more.
  • the above-described molecular weight is preferably 1,000 to 100,000, more preferably 1,500 to 50,000, still more preferably 2,000 to 50,000, and particularly preferably 2,500 to 30,000.
  • the polymer structure included in the constitutional unit A is preferably a polymer structure formed by the constitutional unit GF and a constitutional unit constituting the terminal in the constitutional unit A.
  • the above-described polymer structure is also preferably a polymer structure including all constitutional units GF included in the constitutional unit A and a constitutional unit constituting the terminal.
  • Examples of the above-described constitutional unit constituting the terminal include the same structure as that described in Z A of Formula (A) described later, and a preferred aspect thereof is also the same.
  • Examples of the polymer structure included in the constitutional unit A include a molecular chain formed by a polymer selected from the group consisting of a random copolymer, an alternate copolymer, and a block copolymer.
  • the terminal of the molecular chain of the polymer may be modified with a known modifier.
  • the above-described polymer structure may have crystallinity.
  • a crystallization temperature of the polymer structure is not particularly limited, but from the viewpoint that a composition in which generation of precipitates in a low temperature environment is further suppressed is obtained, the crystallization temperature is preferably lower than 20.0°C and more preferably 17°C or lower.
  • the lower limit value of the crystallization temperature is not particularly limited, but is preferably higher than -20.0°C and more preferably higher than -11.0°C.
  • the crystallization temperature of the above-described polymer structure is intended to be a crystallization temperature measured by a method described in Examples using a differential scanning calorimetry (DSC). That is, the crystallization temperature can be measured as a crystallization temperature of a macromonomer used for synthesis of the constitutional unit A, which will be described later.
  • DSC differential scanning calorimetry
  • the crystallization temperature of the above-described polymer structure may be measured in the same method as described above, after the resin in the composition is hydrolyzed under strong acid or strong base conditions using hydrochloric acid, sodium hydroxide, or the like to separate the polymer structure and obtain a polymer.
  • the constitutional unit GF is a constitutional unit represented by Formula (1-1) or Formula (1-2) described above.
  • the constitutional unit A preferably includes the constitutional unit GF as a repeating unit.
  • the fact that the constitutional unit A includes the constitutional unit GF as a repeating unit means that the constitutional unit A includes a molecular chain formed by repeating a constitutional unit included in the constitutional unit GF.
  • One of preferred aspects is an aspect in which the constitutional unit A includes a molecular chain formed by repeating only the constitutional unit corresponding to the constitutional unit GF.
  • the number of repetitions of the constitutional unit GF (in a case where the constitutional unit A includes a plurality of constitutional units GF, the total number of repetitions is preferably 5 to 100, more preferably 8 to 60, and still more preferably 10 to 50.
  • R A is preferably a hydrocarbon group, preferably a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a bonding thereof, and more preferably a saturated aliphatic hydrocarbon group.
  • hydrocarbon group may have a substituent as long as the effects of the present invention can be obtained.
  • one of preferred aspects of the present invention is an aspect in which the hydrocarbon group is unsubstituted.
  • an alkylene group having 1 to 20 carbon atoms is preferable, an alkylene group having 2 to 6 carbon atoms is more preferable, and an alkylene group having 4 or 5 carbon atoms is still more preferable.
  • saturated aliphatic hydrocarbon group examples include an ethylene group, a propylene group, a 1-ethylethylene group, a trimethylene group, a 1-methyltrimethylene group, a 1-butyltrimethylene group, a tetramethylene group, a 2-methyltetramethylene group, a 1-tridecyltetramethylene group, a pentamethylene group, a 1-methylpentamethylene group, a 3-methylpentamethylene group, a 1-ethylpentamethylene group, and a 1-decylpentamethylene group, and a tetramethylene group or a pentamethylene group is preferable.
  • aromatic hydrocarbon group an aromatic hydrocarbon group having 6 to 20 carbon atoms is preferable, a phenylene group or a naphthylene group is more preferable, and a phenylene group is still more preferable.
  • R B is preferably a hydrocarbon group, preferably a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a bonding thereof, and more preferably a saturated aliphatic hydrocarbon group.
  • hydrocarbon group may have a substituent as long as the effects of the present invention can be obtained.
  • one of preferred aspects of the present invention is an aspect in which the hydrocarbon group is unsubstituted.
  • an alkylene group having 1 to 20 carbon atoms is preferable, and an alkylene group having 2 to 6 carbon atoms is more preferable.
  • saturated aliphatic hydrocarbon group examples include an ethylene group, a propylene group, a 1-ethylethylene group, a trimethylene group, a 1-methyltrimethylene group, and a tetramethylene group, and an ethylene group or a propylene group is preferable.
  • the propylene group refers to a group in which one hydrogen atom of four hydrogen atoms in the ethylene group is substituted with a methyl group.
  • aromatic hydrocarbon group an aromatic hydrocarbon group having 6 to 20 carbon atoms is preferable, a phenylene group or a naphthylene group is more preferable, and a phenylene group is still more preferable.
  • the constitutional unit A contains a constitutional unit L1 represented by Formula (1) and a constitutional unit L2 selected from the group consisting of a constitutional unit represented by Formula (2) and a constitutional unit represented by Formula (3).
  • the constitutional unit represented by Formula (3) corresponds to a constitutional unit formed by linking two constitutional units represented by Formula (1-1).
  • R 1 represents an alkylene group
  • n represents 0 or 1.
  • R 2 represents an alkylene group different from R 1
  • m represents 0 or 1.
  • R 3 's each independently represent an alkyl group.
  • the alkylene group represented by R 1 is not particularly limited, but is preferably a linear or branched alkylene group having 1 to 20 carbon atoms, and from the viewpoint that the composition has more excellent effects of the present invention, more preferably a linear or branched alkylene group having 2 to 16 carbon atoms and still more preferably a linear or branched alkylene group having 3 to 12 carbon atoms.
  • n 0 or 1.
  • R 2 in Formula (2) represents an alkylene group different from R 1 .
  • the different alkylene group means that at least one of different number of carbon atoms or different branching states is satisfied.
  • the alkylene group represented by R 2 is not particularly limited, but from the viewpoint that the composition has more excellent effects of the present invention, is preferably a linear or branched alkylene group having 1 to 20 carbon atoms and more preferably a linear or branched alkylene group having 2 to 16 carbon atoms.
  • m 0 or 1.
  • the numbers of carbon atoms in R 1 and R 2 are different from each other, it does not matter which one of the number of carbon atoms in the alkylene group represented by R 1 and the number of carbon atoms in the alkylene group represented by R 2 is larger, and examples thereof include an aspect in which the number of carbon atoms in the alkylene group represented by R 1 is larger than the number of carbon atoms in the alkylene group represented by R 2 . In this case, the number of carbon atoms in the alkylene group represented by R 1 is 2 or more.
  • branching states of R 1 and R 2 are different from each other refers to an aspect in which the alkylene group represented by R 1 is linear and the alkylene group represented by R 2 is branched, an aspect in which the alkylene group represented by R 1 is branched and the alkylene group represented by R 2 is linear, or an aspect in which the alkylene groups represented by R 1 and R 2 are each branched and at least one of the number or form of branches (for example, position of branching) is different.
  • n in Formula (1) and m in Formula (2) are equal to each other. That is, it is more preferable that, in a case where n is 0, m is also 0, and in a case where n is 1, m is also 1. Among these, it is still more preferable that n and m are 1. In a case where n is equal to m, it is easier to produce a compound which can be the above-described constitutional unit A by polymerization.
  • the compound which can be the constitutional unit A by polymerization herein refers to a compound as a raw material for producing the resin A, which can be the constitutional unit A by polymerization (hereinafter, also referred to as a "macromonomer").
  • the constitutional unit L 2 may be a constitutional unit represented by Formula (3).
  • R 3 represents an alkyl group, and two R 3 's in the constitutional unit may be the same or different from each other.
  • the alkyl group is not particularly limited, but for example, is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, and from the viewpoint that the composition has more excellent effects of the present invention, more preferably an alkyl group having 1 to 10 carbon atoms, still more preferably an alkyl group having 1 to 5 carbon atoms, and particularly preferably an alkyl group having 1 to 3 carbon atoms. Among these, a methyl group is preferable.
  • the constitutional unit L1 and the constitutional unit L2 are preferably constitutional units obtained by ring-opening polymerization of a cyclic compound.
  • cyclic compound a known compound can be used.
  • a compound which can be ring-opened by hydrolysis is preferable, and examples thereof include cyclic amide compounds such as ⁇ -caprolactam; cyclic urea derivatives such as N,N'-dimethylpropylene urea and 1,3-dimethyl-2-imidazolidinone; cyclic esters (lactone compounds) such as ⁇ -propiolactone, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -caprilolactone, ⁇ -valerolactone, ⁇ -methyl- ⁇ -valerolactone, ⁇ -stearolactone, ⁇ -caprolactone, ⁇ -octanoic lactone, 2-methyl- ⁇ -caprolactone, 4-methyl- ⁇ -caprolactone, ⁇ -caprylolactone, ⁇ -palmitolactone
  • a lactone compound or lactide is preferable, and from the viewpoint of higher reactivity and easier availability of raw material, a lactone compound is more preferable and at least one selected from the group consisting of ⁇ -propiolactone, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -caprilolactone, ⁇ -valerolactone, ⁇ -methyl- ⁇ -valerolactone, ⁇ -stearolactone, ⁇ -caprolactone, 2-methyl- ⁇ -caprolactone, 4-methyl- ⁇ -caprolactone, ⁇ -caprylolactone, and ⁇ -palmitolactone is still more preferable.
  • the constitutional unit represented by Formula (2) is included as the above-described constitutional unit L2, and R 1 in Formula (1) and R 2 in Formula (2) are each an ethylene group, a propylene group, a 1-ethylethylene group, a trimethylene group, a 1-methyltrimethylene group, a 1-butyltrimethylene group, a tetramethylene group, a 2-methyltetramethylene group, a 1-tridecyltetramethylene group, a pentamethylene group, a 1-methylpentamethylene group, a 3-methylpentamethylene group, a 1-ethylpentamethylene group, or a 1-decylpentamethylene group, and it is more preferable to be each an ethylene group, a propylene group, a tetramethylene group, or a pentamethylene group.
  • constitutional unit GF examples include the following constitutional units, but the present invention is not limited thereto.
  • *'s each independently represent a bonding site with other structures.
  • the resin A is preferably a comb-shaped polymer (graft polymer) or a star polymer, and more preferably a comb-shaped polymer.
  • the molecular chain (the above-described polymer structure) included in the above-described constitutional unit A is a resin having a side chain (graft chain). This is because the molecular chain in the resin A is less likely to be compatible with other resins or polymerizable monomers (film-forming component), and the phase-separated structure is likely to be formed in the film to be obtained.
  • the formula weight is 1,000 or more, it is more preferable that the number of atoms excluding hydrogen atoms is in a range of 40 to 10,000, it is still more preferable that the number of atoms excluding hydrogen atoms is in a range of 50 to 2,000, and it is particularly preferable that the number of atoms excluding hydrogen atoms is in a range of 60 to 500.
  • the resin A can be produced by polymerizing and/or copolymerizing a macromonomer having a predetermined molecular chain and having a reactive double bond group. According to such an aspect, a comb-shaped polymer is obtained.
  • the above-described macromonomer include a modified poly(meth)acrylate having the above-described molecular chain at the terminal.
  • the resin A can also be produced by reacting the above-described macromonomer with a compound having a branch point and one or more sulfur atoms.
  • a star polymer is obtained.
  • the molecular chain included in the constitutional unit A may be included as P 1 in a resin having a structure same as that represented by Formula (SP-1) described later.
  • the constitutional unit A is preferably a constitutional unit based on a macromonomer represented by Formula (a).
  • R 4 , R 5 , and R 6 each independently represent a hydrogen atom, a halogen atom, or an alkyl group, and among these, a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, or the like) is preferable.
  • R 4 , R 5 , and R 6 are more preferably each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and still more preferably each independently a hydrogen atom or a methyl group.
  • R 5 and R 6 are each particularly preferably a hydrogen atom.
  • X A in Formula (a) represents a single bond or a divalent linking group.
  • the divalent linking group include a divalent aliphatic group (for example, an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, or a substituted alkynylene group), a divalent aromatic group (for example, an arylene group or a substituted arylene group), a divalent heterocyclic group, a sulfur atom (-S-), an imino group (-NH-), a substituted imino bond (-NR 41 '-, where R 41 ' is an aliphatic group, an aromatic group, or a heterocyclic group), a carbonyl bond (-CO-), and a combination thereof.
  • a divalent aliphatic group for example, an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an al
  • the divalent aliphatic group may have a cyclic structure or a branched structure.
  • the number of carbon atoms in the aliphatic group is preferably 1 to 20, more preferably 1 to 15, and still more preferably 1 to 10.
  • a saturated aliphatic group is preferable to an unsaturated aliphatic group.
  • the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxy group, an aromatic group, and a heterocyclic group.
  • the number of carbon atoms in the divalent aromatic group is preferably 6 to 20, more preferably 6 to 15, and still more preferably 6 to 10.
  • the aromatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxy group, an aliphatic group, an aromatic group, and a heterocyclic group.
  • the divalent heterocyclic group preferably has a 5-membered ring or a 6-membered ring as a heterocyclic ring.
  • the heterocyclic ring may be fused with one or more of other heterocyclic rings, aliphatic rings or aromatic rings.
  • L A1 and L A2 each represent the above-described constitutional unit L1 and constitutional unit L2.
  • the arrangement of L A1 and L A2 in Formula (a) does not indicate the arrangement order of the constitutional unit L1 and the constitutional unit L2, and in a case where the number of repetitions of the constitutional unit L1 and the constitutional unit L2 p and q, the arrangement order is not limited. That is, the arrangement order of the constitutional unit L1 and the constitutional unit L2 may be random, alternate, or block.
  • the constitutional unit L2 may be bonded to the left terminal group in Formula (A), or the constitutional unit L1 may be bonded to the right terminal group in Formula (A).
  • the arrangement order of the constitutional unit L1 and the constitutional unit L2 is preferably random or alternate.
  • the arrangement order of the constitutional unit L1 and the constitutional unit L2 is random or alternate, it is presumed that three-dimensional regularity of the molecular chain of the resin A is further lowered, and the crystallinity of the resin A is further lowered.
  • p and q each represent an integer of 1 or more.
  • the range of p is preferably 1 to 120 and more preferably 2 to 60.
  • the range of q is preferably 1 to 120 and more preferably 2 to 60.
  • Z A represents a monovalent organic group.
  • the type of the organic group is not particularly limited, but specific examples thereof include an alkyl group, a hydroxy group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group, and an amino group.
  • the organic group represented by Z A preferably has a steric repulsion effect, and an alkyl group or alkoxy group having 5 to 24 carbon atoms is preferable, and a branched alkyl group having 5 to 24 carbon atoms, a cyclic alkyl group having 5 to 24 carbon atoms, or an alkoxy group having 5 to 24 carbon atoms is particularly preferable.
  • An alkyl group included in the alkoxy group may be linear, branched, or cyclic.
  • the constitutional unit A is preferably a constitutional unit represented by Formula (A).
  • a preferred aspect of the present invention is an aspect in which the constitutional unit A is a constitutional unit represented by Formula (A) and the constitutional unit B is a constitutional unit represented by Formula (B) described later.
  • R 4 represents a hydrogen atom or an alkyl group
  • X A represents a single bond or a divalent linking group
  • p and q each represent an integer of 1 or more
  • Z A represents a hydrogen atom or a monovalent organic group
  • L A1 and L A2 each represent the constitutional unit L1 and the constitutional unit L2.
  • R 4 is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, or the like).
  • X A , L A1 , L A2 , p, q, and Z A in Formula (A) are the same as X A , L A1 , L A2 , p, q, and Z A in Formula (a).
  • the sum of p and q in Formula (a) and Formula (A) is preferably more than 5 and less than 120.
  • p+q is more than the lower limit value
  • the composition has more excellent temporal stability.
  • p+q is less than the upper limit value
  • the composition has more suppressed generation of precipitates in a low temperature environment and more excellent temporal stability.
  • a composition having more excellent developability can be obtained.
  • a content of the constitutional unit L1 in the constitutional unit A is not particularly limited, but from the viewpoint that the effects of the present invention are more excellent, is preferably 2 to 98 mass% and more preferably 5 to 95 mass% with respect to the total mass of the constitutional unit A.
  • a content of the constitutional unit L2 in the constitutional unit A is not particularly limited, but from the viewpoint that the effects of the present invention are more excellent, is preferably 2 to 98 mass% and more preferably 5 to 95 mass% with respect to the total mass of the constitutional unit A.
  • a mass ratio of the constitutional unit L1 to the constitutional unit L2 is more preferably more than 50/50 and less than 95/5. In a case where the above-described mass ratio is within the above-described range, the generation of precipitates in the composition is further suppressed in a low temperature environment. In addition, the composition has more excellent developability. In addition, the above-described mass ratio is still more preferably more than 50/50 and less than 90/10. In a case where the above-described mass ratio is less than the upper limit value, the composition has more excellent temporal stability.
  • the formula weight of the constitutional unit A is preferably 1,000 to 30,000 and more preferably 1,200 to 20,000. In a case where the formula weight is the upper limit value or less, the composition has more excellent temporal stability. On the other hand, in a case of being the lower limit value or more, the composition has more excellent effects of the present invention and has more excellent temporal stability.
  • the above-described formula weight corresponds to a weight-average molecular weight of the macromonomer.
  • the weight-average molecular weight of the macromonomer can be measured by a gel permeation chromatography (GPC) method.
  • the weight-average molecular weight is measured by a GPC method described in detail later.
  • the constitutional unit B is a constitutional unit of the resin A, and has an acidic group in its structure. Having an acidic group in the structure means that the resin A has an acidic group which does not contribute to the formation of the main chain of the resin A.
  • the acidic group is a functional group which meet at least one of definitions of Bronstead acid and Lewis acid and a derivative group thereof (for example, a functional group having a salt structure thereof), and examples thereof include an acidic group selected from a carboxylic acid group, a phosphoric acid group, a sulfonic acid group, a phenolic hydroxy group, and a thiol group, and a derivative group thereof (for example, a salt of the acidic group).
  • the constitutional unit B is preferably a constitutional unit based on a compound having a reactive double bond group (hereinafter, also referred to as a "polymerizable monomer").
  • a compound having a reactive double bond group hereinafter, also referred to as a "polymerizable monomer”.
  • the above-described reactive double bond group and acidic group may be directly linked, or may be bonded through a linking group.
  • the constitutional unit B may be included as a structure same as A 1 in a structure represented by Formula (SP-1) described later.
  • the constitutional unit B refers to a constitutional unit different from the above-described constitutional unit A, and a constitutional unit C and a constitutional unit D described later.
  • the constitutional unit B Since the constitutional unit B has an acidic group, the constitutional unit B can form an interaction with the white particles. In particular, by having an alkali-soluble group such as a carboxylic acid group as the acidic group, it is possible to impart more excellent developability to the resin A for pattern formation by development.
  • the resin A contains the constitutional unit having an acidic group, the resin A is more compatible with the solvent, and application properties of the composition to the support tends to be improved.
  • the acidic group which is a functional group capable of forming interaction with the white particles is, for example, a carboxylic acid group, a phosphoric acid group, a sulfonic acid group, a phenolic hydroxy group, or a thiol group, and at least one of a carboxylic acid group, a sulfonic acid group, or a phosphoric acid group is preferable, and a carboxylic acid group which has good adsorption force to the white particles and a high dispersibility thereof is particularly preferable.
  • the resin A further has a constitutional unit having at least one of a carboxylic acid group, a phosphoric acid group, a sulfonic acid group, a phenolic hydroxy group, or a thiol group.
  • the resin A of the present invention there is no particular limitation on how the acidic group is introduced, but the resin A preferably has one or more constitutional units selected from constitutional units derived from monomers represented by General Formulae (ib) to (iiib).
  • R 4 , R 5 , and R 6 each independently represent a hydrogen atom, a halogen atom, or an alkyl group, and among these, a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, or the like) is preferable.
  • X b in Formula (ib) represents an oxygen atom (-O-) or an imino group (-NH-), and is preferably an oxygen atom.
  • Y b in Formula (iib) represents a methine group or a nitrogen atom.
  • L b represents a single bond or a divalent linking group.
  • the divalent linking group include a divalent aliphatic group (for example, an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, or a substituted alkynylene group), a divalent aromatic group (for example, an arylene group or a substituted arylene group), a divalent heterocyclic group, an oxygen atom (-O-), a sulfur atom (-S-), an imino group (-NH-), a substituted imino bond (-NR 31 '-, where R 31 ' is an aliphatic group, an aromatic group, or a heterocyclic group), a carbonyl bond (-CO-), and a combination thereof.
  • a divalent aliphatic group for example, an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene
  • the divalent aliphatic group may have a cyclic structure or a branched structure.
  • the number of carbon atoms in the aliphatic group is preferably 1 to 20, more preferably 1 to 15, and still more preferably 1 to 10.
  • a saturated aliphatic group is preferable to an unsaturated aliphatic group.
  • the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxy group, an aromatic group, and a heterocyclic group.
  • the number of carbon atoms in the divalent aromatic group is preferably 6 to 20, more preferably 6 to 15, and still more preferably 6 to 10.
  • the aromatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxy group, an aliphatic group, an aromatic group, and a heterocyclic group.
  • the divalent heterocyclic group preferably has a 5-membered ring or a 6-membered ring as a heterocyclic ring.
  • the heterocyclic ring may be fused with one or more of other heterocyclic rings, aliphatic rings or aromatic rings.
  • L b may be a single bond, an alkylene group, or a divalent linking group having an oxyalkylene structure.
  • the oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure.
  • L b may have a polyoxyalkylene structure which includes two or more repeating oxyalkylene structures.
  • As the polyoxyalkylene structure a polyoxyethylene structure or a polyoxypropylene structure is preferable.
  • the polyoxyethylene structure is represented by -(OCH 2 CH 2 ) v -, and v is preferably an integer of 2 or more and more preferably an integer of 2 to 10.
  • Z b represents an acidic group.
  • R 7 , R 8 , and R 9 each independently represent a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, or the like), an alkyl group (for example, a methyl group, an ethyl group, a propyl group, or the like) having 1 to 6 carbon atoms, -Z b , or L b -Z b .
  • L b and Z b have the same meanings as L b and Z b described above, and suitable aspects thereof are also the same.
  • R 7 , R 8 , and R 9 are preferably each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably each independently a hydrogen atom.
  • the monomer represented by Formula (iib) is preferably a compound in which R 4 is a hydrogen atom or a methyl group, L b is an alkylene group, Z b is a carboxylic acid group, and Y b is a methine group.
  • the monomer represented by Formula (iiib) is preferably a compound in which R 7 , R 8 , and R 9 are each independently a hydrogen atom or a methyl group and Z b is a carboxylic acid group.
  • Examples of the above-described monomer include methacrylic acid, crotonic acid, isocrotonic acid, a reaction product of a compound (for example, 2-hydroxyethyl methacrylate) having an addition polymerizable double bond and a hydroxy group in a molecule with a succinic acid anhydride, a reaction product of a compound having an addition polymerizable double bond and a hydroxy group in a molecule with a phthalic acid anhydride, a reaction product of a compound having an addition polymerizable double bond and a hydroxy group in a molecule with a tetrahydroxyphthalic acid anhydride, a reaction product of a compound having an addition polymerizable double bond and a hydroxy group in a molecule with trimellitic acid anhydride, a reaction product of a compound having an addition polymerizable double bond and a hydroxy group in a molecule with a pyromellitic acid anhydride, acrylic acid, an acrylic acid dimer, an
  • the constitutional unit B is preferably a constitutional unit represented by Formula (B).
  • R 4 represents a hydrogen atom or an alkyl group
  • X B represents a single bond or a divalent linking group
  • Z B represents a hydrogen atom, an acidic group selected from the group consisting of a carboxy group, a phosphoric acid group, a sulfonic acid group, a phenolic hydroxy group, and a thiol group, or a derivative group of these groups, and in a case where Z B is a hydrogen atom, X B represents a single bond.
  • R 4 is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, or the like).
  • a suitable aspect of the divalent linking group as X B is the same as L b described above. That is, in a case where X B is a divalent linking group, an alkylene group or an oxyalkylene structure may be included.
  • the oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure.
  • X B may have a polyoxyalkylene structure which includes two or more repeating oxyalkylene structures.
  • As the polyoxyalkylene structure a polyoxyethylene structure or a polyoxypropylene structure is preferable.
  • the polyoxyethylene structure is represented by -(OCH 2 CH 2 ) v -, and v is preferably an integer of 2 or more and more preferably an integer of 2 to 10.
  • the resin A used in the present invention may contain a hydrophobic constitutional unit as the constitutional unit C as long as the effects of the present are exhibited.
  • the hydrophobic constitutional unit does not have the constitutional unit A containing the constitutional unit L1 and the constitutional unit L2, and does not have the acidic group.
  • hydrophobic constitutional unit a constitutional unit derived from (corresponding to) a compound (monomer) having a ClogP value of 1.2 or more is preferable, and a constitutional unit derived from a compound having a ClogP value of 1.2 to 8 is more preferable.
  • the ClogP value is a value calculated by a program "CLOGP” available from Daylight Chemical Information System, Inc. This program provides a value of "calculated logP” calculated by the fragment approach (see the following documents) of Hansch and Leo.
  • the fragment approach is based on a chemical structure of a compound, which estimates the logP value of the compound by dividing the chemical structure into partial structures (fragments) and summing up the logP contributions assigned to the fragments. Details of the method are described in the following documents.
  • a ClogP value calculated by a program CLOGP v4.82 is used.
  • Coil represents a molar concentration of a compound in an oil phase
  • Cwater represents a molar concentration of the compound in a water phase.
  • the value of logP has a negative correlation with the water solubility of an organic compound and is widely used as a parameter for estimating the hydrophilicity and hydrophobicity of an organic compound.
  • hydrophobic constitutional unit it is preferable to have one or more constitutional units selected from constitutional units based on monomers represented by General Formulae (i) to (iii).
  • R 4 , R 5 , and R 6 each independently represent a hydrogen atom, a halogen atom, or an alkyl group, and among these, a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, or the like) is preferable.
  • X c and L c each have the same meanings as X b and L b contained in the constitutional unit B described above, and suitable aspects thereof are also the same.
  • Z c include an aliphatic group (for example, an alkyl group, a substituted alkyl group, an unsaturated alkyl group, or a substituted unsaturated alkyl group), an aromatic group (for example, an aryl group, a substituted aryl group, an arylene group, or a substituted arylene group), a heterocyclic group, and a combination thereof.
  • These groups may include an oxygen atom (-O-), a sulfur atom (-S-), an imino group (-NH-), a substituted imino group (-NR 31 -, where R 31 is an aliphatic group, an aromatic group, or a heterocyclic group), or a carbonyl group (-CO-).
  • the aliphatic group may have a cyclic structure or a branched structure.
  • the number of carbon atoms in the aliphatic group is preferably 1 to 20, more preferably 1 to 15, and still more preferably 1 to 10.
  • the aliphatic group further includes a ring assembly hydrocarbon group or a crosslinked cyclic hydrocarbon group, and examples of the ring assembly hydrocarbon group include a bicyclohexyl group, a perhydronaphthalenyl group, a biphenyl group, and a 4-cyclohexylphenyl group.
  • Examples of the crosslinked cyclic hydrocarbon ring include a bicyclic hydrocarbon ring such as pinane, bornane, norpinane, norbornane, and bicyclooctane rings (a bicyclo[2.2.2]octane ring, a bicyclo[3.2.1]octane ring, or the like); a tricyclic hydrocarbon ring such as homobredane, adamantane, tricyclo[5.2.1.0 2,6 ]decane, and tricyclo[4.3.1.1 2,5 ]undecane rings; and a tetracyclic hydrocarbon ring such as tetracyclo[4.4.0.1 2,5 .1 7,10 ]dodecane and perhydro-1,4-methano-5,8-methanonaphthalene rings.
  • a bicyclic hydrocarbon ring such as pinane, bornane, norpinane, norbornane, and bicyclooctane rings (a bicycl
  • the crosslinked cyclic hydrocarbon ring also includes a fused cyclic hydrocarbon ring, for example, a fused ring in which a plurality of 5- to 8-membered cycloalkane rings, such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, and perhydrophenalene rings, are fused.
  • a fused cyclic hydrocarbon ring for example, a fused ring in which a plurality of 5- to 8-membered cycloalkane rings, such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, and perhydrophenalene rings, are fused.
  • the aliphatic group a saturated aliphatic group is preferable to an unsaturated aliphatic group.
  • the aliphatic group may have a substituent.
  • the substituent include a halogen atom, an aromatic group, and a heterocyclic group.
  • the aliphatic group does not have an acidic group as a substituent.
  • the number of carbon atoms in the aromatic group is preferably 6 to 20, more preferably 6 to 15, and still more preferably 6 to 10.
  • the aromatic group may have a substituent.
  • the substituent include a halogen atom, an aliphatic group, an aromatic group, and a heterocyclic group.
  • the aromatic group does not have an acidic group as a substituent.
  • the heterocyclic group preferably has a 5-membered ring or a 6-membered ring as a heterocyclic ring.
  • the heterocyclic ring may be fused with another heterocyclic ring, an aliphatic ring, or an aromatic ring.
  • the heterocyclic group does not have an acidic group as a substituent.
  • R 7 , R 8 , and R 9 each independently represent a hydrogen atom, a halogen atom (for example, fluorine, chlorine, bromine, or the like), an alkyl group (for example, a methyl group, an ethyl group, a propyl group, or the like) having 1 to 6 carbon atoms, Z C , or -L C -Z C .
  • L C and Z C have the same meanings as those in the above.
  • R 7 , R 8 , and R 9 are each preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom.
  • the monomer represented by Formula (ic) is preferably a compound in which R 4 , R 5 , and R 6 are each a hydrogen atom or a methyl group, L c is a single bond, an alkylene group, or a divalent linking group having an oxyalkylene structure, X c is an oxygen atom or an imino group, and Z c is an aliphatic group, a heterocyclic group, or an aromatic group.
  • the monomer represented by Formula (iic) is preferably a compound in which R 4 is a hydrogen atom or a methyl group, L c is an alkylene group, and Z c is an aliphatic group, a heterocyclic group, or an aromatic group.
  • the monomer represented by Formula (iiic) is preferably a compound in which R 7 , R 8 , and R 9 are each a hydrogen atom or a methyl group, and Z c is an aliphatic group, a heterocyclic group, or an aromatic group.
  • the monomers represented by Formulae (ic) to (iiic) are more preferably the compound represented by Formula (ic).
  • a compound in which, in Formula (ic), R 4 is a hydrogen atom or a methyl group, R 5 and R 6 are hydrogen atoms, L c is a single bond, X c is an oxygen atom, Z c is an aromatic group ((meth)acrylic acid esters) is still more preferable, and from the viewpoint that the composition has more excellent hydrophobicity and has more excellent effects of the present invention, benzyl (meth)acrylate is most preferable.
  • Examples of typical compounds represented by Formulae (ic) to (iiic) include radically polymerizable compounds selected from acrylic acid esters, methacrylic acid esters, and styrenes.
  • the resin A may further have other constitutional units D having various functions (for example, a constitutional unit which has a functional group having an affinity with a dispersion medium used for the dispersion), which is different from the constitutional unit A, the constitutional unit B, and the constitutional unit C.
  • constitutional units D having various functions (for example, a constitutional unit which has a functional group having an affinity with a dispersion medium used for the dispersion), which is different from the constitutional unit A, the constitutional unit B, and the constitutional unit C.
  • constitutional units derived from radically polymerizable compounds selected from acrylonitriles and methacrylonitriles examples include constitutional units derived from radically polymerizable compounds selected from acrylonitriles and methacrylonitriles.
  • the resin A may be a resin having a polymerizable group (polymerizable resin).
  • the polymerizable group include an ethylenically unsaturated bond-containing group, an epoxy group, a cyclic ether group such as an oxetane group, a methylol group, an alkoxymethyl group, and a blocked isocyanate group.
  • Examples of the above-described ethylenically unsaturated bond-containing group include a vinyl group, a vinyloxy group, an allyl group, a methallyl group, a (meth)acryloyl group, a styrene group (vinylphenyl group), a cinnamoyl group, and a maleimide group.
  • a (meth)acryloyl group, a styrene group, or a maleimide group is preferable, a (meth)acryloyl group is more preferable, and an acryloyl group is particularly preferable.
  • an amount of the polymerizable group included in 1 g of the resin A is preferably 0.01 to 5.0 mmol/g.
  • the upper limit is more preferably 4.0 mmol/g or less, still more preferably 3.0 mmol/g or less, even more preferably 2.0 mmol/g or less, and particularly preferably 1.5 mmol/g or less.
  • the lower limit is preferably 0.1 mmol/g or more and more preferably 0.2 mmol/g or more.
  • the above-described polymerizable group value of the polymerizable resin can be calculated by the same method as a method for calculating a polymerizable group value of a resin B described later.
  • the resin A is a resin having a polymerizable group
  • the resin A may include a constitutional unit having a polymerizable group as the above-described constitutional unit D.
  • the polymerizable group in the constitutional unit A, may be included as any of Z 1 , A 1 , or P 1 in a resin having a structure same as that represented by Formula (SP-1) described later, but it is preferably included in P 1 and is preferably included in P 1 as the constitutional unit D.
  • constitutional unit D is a constitutional unit having a polymerizable group
  • constitutional unit D is included as a repeating unit.
  • Preferred examples of such a repeating unit include a repeating unit represented by Formula (A-1-1) described later.
  • the constitutional unit D is a constitutional unit having a polymerizable group
  • the constitutional unit D is introduced by using a monomer having a polymerizable group (for example, glycidyl methacrylate, (3-ethyloxetan-3-yl) methacrylate, and the like) as a monomer.
  • a monomer having a polymerizable group for example, glycidyl methacrylate, (3-ethyloxetan-3-yl) methacrylate, and the like
  • the above-described constitutional unit D is introduced by polymerizing a monomer to obtain a resin, and then reacting a compound having a group which reacts with the acidic group included in the constitutional unit B and having a polymerizable group with the resin.
  • the constitutional unit B has a carboxy group as the acidic group
  • a part of the constitutional unit B can be changed to the constitutional unit D having an ethylenically unsaturated bond-containing group.
  • the constitutional unit B has a phenolic hydroxy group as the acidic group
  • a part of the constitutional unit B can be changed to the constitutional unit D having an ethylenically unsaturated bond-containing group.
  • the resin contains a constitutional unit which has a group capable of reacting with an isocyanato group, such as a hydroxy group
  • a polymerizable group can be introduced into at least a part of the group capable of reacting with an isocyanato group, and the constitutional unit may be designated as the constitutional unit D.
  • the resin A containing the constitutional unit D by a method such as that a constitutional unit derived from 2-(2-bromoisobutyryloxy)ethyl methacrylate is introduced into the resin and a methacryloxy group is introduced by allowing a base to act on the resin to remove HBr.
  • constitutional unit D includes the following structures, but the present invention is not limited thereto.
  • the resin A can be synthesized based on a known method, and examples of a solvent used for synthesizing the resin A include ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol, butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, toluene, ethyl acetate, methyl lactate, and ethyl lactate.
  • the solvent may be used alone or in combination of two or more kinds thereof.
  • a content of the above-described constitutional unit A is preferably 3 to 90 mass%, more preferably 10 to 90 mass%, and still more preferably 30 to 80 mass% with respect to the total mass of the resin A.
  • the composition has more excellent effects of the present invention.
  • a content of the above-described constitutional unit B is preferably 3 to 90 mass%, more preferably 10 to 90 mass%, and still more preferably 10 to 60 mass% with respect to the total mass of the resin A.
  • the content of the constitutional unit B is within the above-described range, the composition has more excellent effects of the present invention.
  • a content of the above-described constitutional unit C is preferably 3 to 90 mass%, more preferably 5 to 60 mass%, and still more preferably 10 to 40 mass% with respect to the total mass of the resin A. In a case where the content of the constitutional unit C is within the above-described range, the composition has excellent pattern forming property.
  • a content of the above-described constitutional unit D is preferably 0 to 80 mass% and more preferably 10 to 60 mass% with respect to the total mass of the resin A. In a case where the content of the constitutional unit D is within the above-described range, the composition has excellent pattern forming property.
  • the content of the above-described constitutional unit A is 10 to 90 mass% with respect to the total mass of the above-described resin A and the above-described constitutional unit B is 10 to 90 mass% with respect to the total mass of the above-described resin A.
  • Each constitutional unit may be used singly or in combination of two or more thereof.
  • a weight-average molecular weight of the resin A is preferably 2,000 to 300,000, more preferably 10,000 to 200,000, still more preferably 12,000 to 100,000, and particularly preferably 15,000 to 50,000. In a case where the weight-average molecular weight of the resin A is within the above-described range, the composition has more excellent effects of the present invention.
  • the weight-average molecular weight of the resin A is measured by a method specifically described in Examples.
  • An acid value of the resin A is preferably 10 to 250 mgKOH/g, more preferably 20 to 200 mgKOH/g, and particularly preferably 30 to 180 mgKOH/g.
  • the acid value of the resin A is within the above-described range, a composition having more excellent developability can be obtained. Furthermore, the precipitation of the white particles can be further suppressed, the number of coarse particles can be further reduced, and the temporal stability of the composition is further improved.
  • the acid value of the resin can be calculated, for example, from an average content of acidic groups in the resin.
  • a resin having a desired acid value can be obtained by changing the content of the constitutional unit containing an acidic group, which is a constitutional unit of the resin.
  • the acid value can be determined by a neutralization titration using a sodium hydroxide aqueous solution. Specifically, the acid value can be determined by dissolving the resin in a solvent, titrating the solution with a sodium hydroxide aqueous solution using a potential difference measurement method to calculate an amount of the acid included in 1 g of solid content of the resin, and then converting the value to a KOH equivalent.
  • a solubility parameter (SP value) of the resin A is preferably 20.00 to 21.00 MPa 0.5 , more preferably 20.05 to 20.90 MPa 0.5 , and still more preferably 20.10 to 20.70 MPa 0.5 .
  • the resin A is a binder
  • 20.00 to 21.00 MPa 0.5 is preferable
  • 20.05 to 20.90 MPa 0.5 is more preferable
  • 20.10 to 20.70 MPa 0.5 is still more preferable.
  • the resin A is a dispersant
  • 20.00 to 21.00 MPa 0.5 is preferable
  • 20.40 to 20.95 MPa 0.5 is more preferable
  • 20.50 to 20.90 MPa 0.5 is still more preferable.
  • the SP value of the above-described polymer structure included in the constitutional unit A is preferably 17.61 to 20.06 MPa 0.5 , more preferably 18.02 to 19.65 MPa 0.5 , and still more preferably 18.43 to 19.24 MPa 0.5 .
  • the SP value of the above-described polymer structure included in the constitutional unit A (preferably, as the SP value of the polymer structure composed of the constitutional unit GF and the terminal structure), it is preferable that a difference between the SP value of the above-described polymer structure included in the constitutional unit A and the SP value of the solvent is a value within a range described later.
  • a value according to the Okitsu method is used as the value of the solubility parameter (SP value).
  • SP value solubility parameter
  • documents describing the Okitsu method Toshinao Okitsu, The Journal of The Adhesion Society of Japan, vol. 29, No. 5, 204-211 (1993 ) or SP Value, Fundamentals-Applications and Calculation Method (Yamamoto, JOHOKIKO, CO., LTD., 2005) is referred to.
  • measurement may be performed by another method.
  • resin A examples include resin A-1 to resin A-36, resin A-101, and resin A-102 in Examples, but the present invention is not limited thereto.
  • the above-described resin A can be synthesized by a known method.
  • a content of the resin A in the composition is preferably 1 to 70 mass% and more preferably 5 to 50 mass%, and from the viewpoint that the composition has more excellent effects of the present invention, still more preferably 10 to 40 mass%.
  • the content of the resin A in the composition is preferably 0.1 to 50 mass% and more preferably 0.3 to 40 mass%, and from the viewpoint that a composition having more excellent developability is obtained, still more preferably 0.5 to 30 mass%.
  • the dispersibility of the white particles is also better.
  • the film-forming component in the composition according to the embodiment of the present invention further includes a resin B which is a resin different from the above-described resin A.
  • the resin B is a resin which does not correspond to the resin A, and is, for example, a resin which does not have the constitutional unit A including a constitutional unit GF or a resin which does not satisfy all of the above-described requirement 1 and requirement 2.
  • the resin B is blended in, for example, an application for dispersing particles in a composition or an application as a binder.
  • applications of the resin B are only exemplary, and the resin can also be used for other purposes in addition to such applications.
  • one of the resin A and the resin B is a dispersant for the above-described particles and the other is a binder.
  • one preferred aspect thereof is an aspect in which the above-described resin A is a binder and the above-described resin B is a dispersant.
  • composition according to the embodiment of the present invention includes the resin as a dispersant in an amount of preferably 10 mass% or more, more preferably 20 mass% or more, and still more preferably 30 mass% or more with respect to the total mass of the resin included as the film-forming component.
  • composition according to the embodiment of the present invention includes the resin as a binder in an amount of preferably 10 to 250 parts by mass, more preferably 20 to 225 parts by mass, and still more preferably 30 to 200 parts by mass with respect to 100 parts by mass of the resin as a dispersant.
  • the composition includes the above-described resin B in an amount of preferably 10 to 250 parts by mass, more preferably 20 to 225 parts by mass, and still more preferably 30 to 200 parts by mass with respect to 100 parts by mass of the above-described resin A.
  • the above-described resin A is a comb-shaped polymer and the above-described resin B is a star polymer.
  • the above-described resin A is a star polymer and the above-described resin B is a comb-shaped polymer.
  • the above-described resin A is a comb-shaped polymer and the above-described resin B is a comb-shaped polymer.
  • the aspect 1 is preferable.
  • the resin A is a binder and the resin B is a dispersant.
  • the resin A is a dispersant and the resin B is a binder.
  • the resin A is a binder and the resin B is a dispersant, or the resin A is a dispersant and the resin B is a binder, and it is more preferable that the resin A is a dispersant and the resin B is a binder.
  • An SP value of the resin B is not particularly limited, but is preferably 19.90 to 21.00 MPa 0.5 .
  • the SP value of the resin B is preferably 20.30 to 21.00 MPa 0.5 , more preferably 20.40 to 20.95 MPa 0.5 , and still more preferably 20.50 to 20.90 MPa 0.5 .
  • the SP value of the resin B is preferably 19.80 to 20.40 MPa 0.5 , more preferably 19.90 to 20.30 MPa 0.5 , and still more preferably 19.95 to 20.25 MPa 0.5 .
  • a difference in SP value between the above-described resin A and the above-described resin B is preferably 0.20 MPa 0.5 or more, more preferably 0.30 MPa 0.5 or more, and still more preferably 0.40 MPa 0.5 or more.
  • the upper limit of the above-described difference in SP value is preferably 1.0 MPa 0.5 or less, more preferably 0.7 MPa 0.5 or less, and still more preferably 0.5 MPa 0.5 or less.
  • the difference in SP value of at least one combination of a certain resin A and a certain resin B is within the above-described range, it is more preferable that the difference between an average SP value in the resin A and an average SP value in the resin B is within the above-described range, and it is still more preferable that the difference in SP value in all combinations of the certain resin A and the certain resin B is within the above-described range.
  • the average SP value in the resin A is calculated as a weighted average value weighted by the mass content of each resin.
  • an average SP value AvSP in the resin A is represented by the following expression.
  • the average SP value in the resin B is calculated in the same manner.
  • the dispersant preferably has a higher SP value than the binder.
  • One of preferred aspects of the present invention is an aspect in which the SP value of the resin B is higher than that of the resin A.
  • the resin B any known resin can be used.
  • the resin include a (meth)acrylic resin, a (meth)acrylamide resin, an epoxy resin, an ene-thiol resin, a polycarbonate resin, a polyether resin, a polyarylate resin, a polysulfone resin, a polyethersulfone resin, a polyphenylene resin, a polyarylene ether phosphine oxide resin, a polyimide resin, a polyamide resin, a polyolefin resin, a cyclic olefin resin, a polyester resin, a styrene resin, a silicone resin, and a urethane resin.
  • a weight-average molecular weight (Mw) of the resin B is preferably 2,000 or more, preferably 3,000 or more, more preferably 4,000 or more, and still more preferably 5,000 or more.
  • the weight-average molecular weight of the resin B is preferably 2,000,000 or less, more preferably 1,000,000 or less, and still more preferably 500,000 or less.
  • a resin having an acidic group can be used as the resin B.
  • the acidic group include a carboxy group, a phosphoric acid group, a sulfo group, and a phenolic hydroxy group. Among these, a carboxy group or a phosphoric acid group is preferable, and a carboxy group is more preferable.
  • the resin having an acidic group can also be used as an alkali-soluble resin or a dispersant.
  • An acid value of the resin having an acidic group is preferably 30 to 500 mgKOH/g. The lower limit is more preferably 50 mgKOH/g or more and still more preferably 70 mgKOH/g or more.
  • the upper limit is more preferably 400 mgKOH/g or less, still more preferably 200 mgKOH/g or less, even still more preferably 150 mgKOH/g or less, and most preferably 120 mgKOH/g or less.
  • resin having an acidic group reference can be made to the description in paragraph “0558” to "0571” of JP2012-208494A (paragraph “0685” to "0700” of the corresponding US2012/0235099A ) and the description in paragraph “0076” to "0099” of JP2012-198408A , the contents of which are incorporated herein by reference.
  • a resin including a repeating unit derived from a compound represented by Formula (ED1) and/or a compound represented by Formula (ED2) (hereinafter, these compounds will also be referred to as an "ether dimer”) can be used.
  • R 1 and R 2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms, which may have a substituent.
  • R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. Specific examples of Formula (ED2) can be found in the description of JP2010-168539A .
  • a resin including a repeating unit derived from a compound represented by Formula (X) can be used as the resin B.
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents an alkylene group having 2 to 10 carbon atoms
  • R 3 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, which may have a benzene ring
  • n represents an integer of 1 to 15.
  • the resin B contains a constitutional unit selected from the group consisting of the constitutional unit represented by Formula (1-1) described above and the constitutional unit represented by Formula (1-2) described above, and it is more preferable to include the constitutional unit represented by Formula (1-1) described above.
  • the resin B is a star polymer.
  • the resin B which is a star polymer may be used as a binder, but is preferably dispersed as a dispersant.
  • star polymer examples include a resin (hereinafter, also referred to as a resin (SP-1)) having a structure represented by Formula (SP-1).
  • the resin (SP-1) can be preferably used as a dispersant, but may also be used as a binder.
  • Z 1 represents an (m+n)-valent linking group
  • At least one of Z 1 , A 1 , or P 1 in Formula (SP-1) may include an ethylenically unsaturated bond-containing group.
  • the ethylenically unsaturated bond-containing group include a vinyl group, a vinyloxy group, an allyl group, a methallyl group, a (meth)acryloyl group, a styrene group, a cinnamoyl group, and a maleimide group.
  • a (meth)acryloyl group, a styrene group, or a maleimide group is preferable, a (meth)acryloyl group is more preferable, and an acryloyl group is particularly preferable.
  • the resin (SP-1) includes the ethylenically unsaturated bond-containing group
  • such a resin corresponds to a polymerizable resin described later. It is sufficient that the ethylenically unsaturated bond-containing group is included in any of Z 1 , A 1 , or P 1 in Formula (SP-1), but it is preferable to be included in P 1 .
  • P 1 is preferably a polymer chain having a repeating unit including the ethylenically unsaturated bond-containing group in the side chain.
  • a 1 represents a group including the above-described substituent.
  • substituent a heterocyclic group, an acidic group, a group having a basic nitrogen atom, a hydrocarbon group having 4 or more carbon atoms, or a hydroxy group is preferable, and an acidic group is more preferable.
  • the acidic group include a carboxy group, a sulfo group, and a phosphoric acid group, and a carboxy group is preferable.
  • a 1 preferably includes 1 to 10 of the above-described substituents, and more preferably includes 1 to 6 of the above-described substituents.
  • a 1 a group which is formed by the above-described substituent and a linking group including 1 to 200 carbon atoms, 0 to 20 nitrogen atoms, 0 to 100 oxygen atoms, 1 to 400 hydrogen atoms, and 0 to 40 sulfur atoms being bonded to each other can be used as the group including the above-described substituent, which is represented by A 1 , a group which is formed by the above-described substituent and a linking group including 1 to 200 carbon atoms, 0 to 20 nitrogen atoms, 0 to 100 oxygen atoms, 1 to 400 hydrogen atoms, and 0 to 40 sulfur atoms being bonded to each other can be used.
  • Examples thereof include a group which is formed by one or more acidic groups being bonded through a chain-like saturated hydrocarbon group having 1 to 10 carbon atoms, a cyclic saturated hydrocarbon group having 3 to 10 carbon atoms, or an aromatic hydrocarbon group having 5 to 10 carbon atoms.
  • the chain-like saturated hydrocarbon group, the cyclic saturated hydrocarbon group, and the aromatic hydrocarbon group may further have a substituent.
  • substituents examples include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 16 carbon atoms, a hydroxy group, a carboxy group, an amino group, a sulfonamide group, an N-sulfonylamide group, an acyloxy group having 1 to 6 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a halogen atom, an alkoxycarbonyl group having 2 to 7 carbon atoms, a cyano group, a carbonate group, and an ethylenically unsaturated bond-containing group.
  • substituent itself may be A'.
  • a chemical formula weight of A 1 is preferably 30 to 2,000.
  • the upper limit is preferably 1,000 or less and more preferably 800 or less.
  • the lower limit is preferably 50 or more and more preferably 100 or more.
  • Z 1 represents an (m+n)-valent linking group.
  • the (m+n)-valent linking group include a group composed of 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 sulfur atoms.
  • Examples of the (m+n)-valent linking group also include a group (which may form a ring structure) composed of the following constitutional unit or a combination of two or more the following constitutional units.
  • the (m+n)-valent linking group may have a substituent.
  • substituents include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 16 carbon atoms, a hydroxy group, an amino group, a carboxy group, a sulfonamide group, an N-sulfonylamide group, an acyloxy group having 1 to 6 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a halogen atom, an alkoxycarbonyl group having 2 to 7 carbon atoms, a cyano group, a carbonate group, and an ethylenically unsaturated bond-containing group.
  • the (m+n)-valent linking group represented by Z 1 is a group represented by any one of the following formulae.
  • L 3 represents a trivalent group.
  • T 3 represents a single bond or a divalent linking group, and in a case where three T 3 's are present, T 3 's may be the same as or different from each other.
  • L 4 represents a tetravalent group.
  • T 4 represents a single bond or a divalent linking group, and in a case where four T 4 's are present, T 4 's may be the same as or different from each other.
  • L 5 represents a pentavalent group.
  • T 5 represents a single bond or a divalent linking group, and in a case where five T 5 's are present, T 5 's may be the same as or different from each other.
  • L 6 represents a hexavalent group.
  • T 6 represents a single bond or a divalent linking group, and in a case where six T 6 's are present, T 6 's may be the same as or different from each other.
  • Examples of the divalent linking group represented by T 3 to T 6 include -CH 2 -, -O-, -CO-, -COO-, -OCO-, -NH-, an aliphatic ring group, an aromatic hydrocarbon ring group, a heterocyclic group, and a group consisting of a combination thereof.
  • the aliphatic ring group, the aromatic hydrocarbon ring group, or the heterocyclic group may be a monocycle or a fused ring.
  • the divalent linking group may further have the above-described substituent.
  • Examples of the trivalent group represented by L 3 include a group obtained by removing one hydrogen atom from the above-described divalent linking group.
  • Examples of the tetravalent group represented by L 4 include a group obtained by removing two hydrogen atoms from the above-described divalent linking group.
  • Examples of the pentavalent group represented by L 5 include a group obtained by removing three hydrogen atoms from the above-described divalent linking group.
  • Examples of the hexavalent group represented by L 6 include a group obtained by removing four hydrogen atoms from the above-described divalent linking group.
  • the trivalent to hexavalent groups represented by L 3 to L 6 may further have the above-described substituent.
  • a chemical formula weight of Z 1 is preferably 20 to 3,000.
  • the upper limit is preferably 2,000 or less and more preferably 1,500 or less.
  • the lower limit is preferably 50 or more and more preferably 100 or more.
  • the chemical formula weight of Z 1 is a value calculated from the structural formula.
  • Y 1 and Y 2 each independently represent a single bond or a linking group.
  • the linking group include a group composed of 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 sulfur atoms.
  • the above-described group may further have the above-described substituent.
  • Specific examples of the linking group represented by Y 1 and Y 2 include a group composed of one of the following constitutional units or a combination of two or more of the constitutional units.
  • P 1 represents a polymer chain.
  • a polymer chain which has, in the main chain, at least one repeating unit selected from a poly(meth)acrylic structural repeating unit, a polyether structural repeating unit, a polyester structural repeating unit, a polyamide structural repeating unit, a polyimide structural repeating unit, a polyimine structural repeating unit, or a polyurethane structural repeating unit is preferable.
  • a polymer chain including a repeating unit represented by Formulae (P1-1) to (P1-5) is preferable.
  • R G1 and R G2 each represent an alkylene group.
  • R G1 and R G2 each represent an alkylene group.
  • a linear or branched alkylene group having 1 to 20 carbon atoms is preferable, a linear or branched alkylene group having 2 to 16 carbon atoms is more preferable, and a linear or branched alkylene group having 3 to 12 carbon atoms is still more preferable.
  • the alkylene group may have a substituent.
  • substituents examples include an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group, and an ethylenically unsaturated bond-containing group.
  • R G3 represents a hydrogen atom or a methyl group.
  • Q G1 represents -O- or -NH-
  • L G1 represents a single bond or an arylene group
  • L G2 represents a single bond or a divalent linking group. It is preferable that Q G1 represents -O-. It is preferable that L G1 represents a single bond.
  • Examples of the divalent linking group represented by L G2 include an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms), -NH-, -SO-, -SO 2 -, -CO-, -O-, -COO-, -OCO-, -S-, -NHCO-, -CONH-, and a group including a combination of two or more thereof.
  • an alkylene group preferably an alkylene group having 1 to 12 carbon atoms
  • an arylene group preferably an arylene group having 6 to 20 carbon atoms
  • R G4 represents a hydrogen atom or a substituent.
  • substituents include an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group, an ethylenically unsaturated bond-containing group, and an acidic group.
  • the repetition number of repeating units in P 1 is preferably 3 to 2,000.
  • the upper limit is preferably 1,500 or less and more preferably 1,000 or less.
  • the lower limit is preferably 5 or more and more preferably 7 or more.
  • P 1 is preferably a polymer chain having a repeating unit including an ethylenically unsaturated bond-containing group in the side chain.
  • the proportion of the repeating unit including an ethylenically unsaturated bond-containing group in the side chain with respect to the total repeating units constituting P 1 is preferably 1 mol% or more, more preferably 2 mol% or more, and still more preferably 3 mol% or more.
  • the upper limit may be 100 mol%.
  • P 1 is a polymer chain having a repeating unit including an ethylenically unsaturated bond-containing group in the side chain
  • P 1 includes other repeating units in addition to the repeating unit including an ethylenically unsaturated bond-containing group in the side chain.
  • the other repeating unit include a repeating unit having an acidic group at a side chain.
  • the proportion of the repeating unit having an acidic group at a side chain with respect to the total repeating units constituting P 1 is preferably 50 mol% or less, more preferably 2 to 48 mol%, and still more preferably 4 to 46 mol%.
  • a weight-average molecular weight of the polymer chain represented by P 1 is preferably 1,000 or more and more preferably 1,000 to 10,000.
  • the upper limit is preferably 9,000 or less, more preferably 6,000 or less, and still more preferably 3,000 or less.
  • the lower limit is preferably 1,200 or more and more preferably 1,400 or more.
  • the weight-average molecular weight of P 1 is a value calculated from the weight-average molecular weight of a raw material used for introducing into the polymer chain.
  • resin (SP-1) examples include polymer compounds C-1 to C-31 described in paragraphs "0196” to “0209” of JP2013-043962A , polymer compounds (C-1) to (C-61) described in paragraphs "0256” to "0269” of JP2014-177613A , and a resin having a structure described in paragraph "0061” of WO2018/163668A , the contents of which are incorporated herein by reference.
  • a comb-shaped polymer can also be used.
  • the resin B is a comb-shaped polymer
  • due to steric hindrance caused by the side chain (graft chain), aggregation and the like of particles in the composition can be suppressed more effectively, and excellent storage stability can be obtained.
  • the resin B including the repeating unit having a graft chain may be used as a dispersant or a binder.
  • the graft chain means a polymer chain branched and extended from the main chain of the comb-shaped polymer.
  • the length of the graft chain is not particularly limited, and in a case where the graft chain is longer, a steric repulsion effect is enhanced, and thus it is possible to improve dispersibility of the particles and facilitate the formation of the phase-separated structure.
  • the number of atoms excluding the hydrogen atoms is preferably 40 to 10,000, the number of atoms excluding the hydrogen atoms is more preferably 50 to 2,000, and the number of atoms excluding the hydrogen atoms is still more preferably 60 to 500.
  • the graft chain includes at least one structural repeating unit selected from a polyester structural repeating unit, a polyether structural repeating unit, a poly(meth)acrylic structural repeating unit, a polyurethane structural repeating unit, a polyurea structural repeating unit, or a polyamide structural repeating unit, it is more preferable that the graft chain includes at least one structural repeating unit selected from a polyester structural repeating unit, a polyether structural repeating unit, or a poly(meth)acrylic structural repeating unit, and it is still more preferable that the graft chain includes a polyester structural repeating unit.
  • polyester structural repeating unit examples include a repeating unit having a structure represented by Formula (G-1), Formula (G-4), or Formula (G-5).
  • polyether structural repeating unit examples include a repeating unit having a structure represented by Formula (G-2).
  • poly(meth)acrylic structural repeating unit examples include a repeating unit having a structure represented by Formula (G-3).
  • R G1 and R G2 each represent an alkylene group.
  • the alkylene group represented by R G1 and R G2 is not particularly limited, but is preferably a linear or branched alkylene group having 1 to 20 carbon atoms, more preferably a linear or branched alkylene group having 2 to 16 carbon atoms, and still more preferably a linear or branched alkylene group having 3 to 12 carbon atoms.
  • R G3 represents a hydrogen atom or a methyl group.
  • Q G1 represents -O- or -NH-
  • L G1 represents a single bond or a divalent linking group.
  • the divalent linking group include an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an alkyleneoxy group (preferably an alkyleneoxy group having 1 to 12 carbon atoms), an oxyalkylenecarbonyl group (preferably an oxyalkylenecarbonyl group having 1 to 12 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms), -NH-, -SO-, -SO 2 -, -CO-, -O-, -COO-, OCO-, -S-, and a group formed by a combination of two or more of these groups.
  • R G4 represents a hydrogen atom or a substituent.
  • substituents include an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, and a heteroarylthioether group.
  • a terminal structure of the graft chain is not particularly limited.
  • the terminal structure may be a hydrogen atom or a substituent.
  • substituent include an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, and a heteroarylthioether group.
  • a group having a steric repulsion effect is preferable, and an alkyl group or alkoxy group having 5 to 24 carbon atoms is preferable.
  • the alkyl group and the alkoxy group may be linear, branched, or cyclic, and are preferably linear or branched.
  • the graft chain is preferably a structure represented by Formula (G-1a), Formula (G-2a), Formula (G-3a), Formula (G-4a), or Formula (G-5a).
  • R G1 and R G2 each independently represent an alkylene group
  • R G3 represents a hydrogen atom or a methyl group
  • Q G1 represents -O- or -NH-
  • L G1 represents a single bond or a divalent linking group
  • R G4 represents a hydrogen atom or a substituent
  • W 100 represents a hydrogen atom or a substituent.
  • n1 to n5 each independently represent an integer of 2 or more.
  • R G1 to R G4 , Q G1 , and L G1 have the same meanings as R G1 to R G4 , Q G1 , and L G1 described in Formulae (G-1) to (G-5), and preferred ranges thereof are also the same.
  • W 100 represents a substituent.
  • the substituent include an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, and a heteroarylthioether group.
  • a group having a steric repulsion effect is preferable, and an alkyl group or alkoxy group having 5 to 24 carbon atoms is preferable.
  • the alkyl group and the alkoxy group may be linear, branched, or cyclic, and are preferably linear or branched.
  • n1 to n5 each are preferably an integer of 2 to 100, more preferably an integer of 2 to 80, and still more preferably an integer of 8 to 60.
  • a plurality of R G1 's in each repeating unit may be the same or different from each other.
  • the arrangement of the repeating units is not particularly limited, and may be performed in any of a random manner, an alternative manner, and a blocked manner. The same applies to Formulae (G-2a) to (G-5a).
  • repeating unit having a graft chain examples include a repeating unit represented by Formula (A-1-2).
  • X 2 represents the main chain of the repeating unit (structure included in the main chain of the comb-shaped polymer), L 2 represents a single bond or a divalent linking group, and W 1 represents a graft chain.
  • Examples of the main chain of the repeating unit represented by X 2 in Formula (A-1-2) include the structures described in the description of X 1 of Formula (A-1-1) described later, and preferred ranges thereof are also the same.
  • Examples of the divalent linking group represented by L 2 in Formula (A-1-2) include an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms), -NH-, -SO-, -SO 2 -, -CO-, -O-, -COO-, -OCO-, -S-, and a group formed by a combination of two or more of these groups.
  • Examples of the graft chain represented by W 1 in Formula (A-1-2) include the graft chains described above.
  • repeating unit represented by Formula (A-1-2) include a repeating unit represented by Formula (A-1-2a) and a repeating unit represented by Formula (A-1-2b).
  • R b1 to R b3 each independently represent a hydrogen atom or an alkyl group
  • Q b1 represents -CO-, -COO-, -OCO-, -CONH-, or a phenylene group
  • L 2 represents a single bond or a divalent linking group
  • W 1 represents a graft chain.
  • the number of carbon atoms in the alkyl group represented by R b1 to R b3 is preferably 1 to 10, more preferably 1 to 3, and still more preferably 1.
  • Q b1 is preferably -COO- or -CONH- and more preferably -COO-.
  • R b10 and R b11 each independently represent a hydrogen atom or an alkyl group
  • m2 represents an integer of 1 to 5
  • L 2 represents a single bond or a divalent linking group
  • W 1 represents a graft chain.
  • the number of carbon atoms in the alkyl group represented by R b10 and R b11 is preferably 1 to 10 and more preferably 1 to 3.
  • a weight-average molecular weight (Mw) of the repeating unit having a graft chain is preferably 1,000 or more, more preferably 1,000 to 10,000, and still more preferably 1,000 to 7,500.
  • the weight-average molecular weight of the repeating unit having a graft chain is a value calculated from the weight-average molecular weight of the raw material monomer used for the polymerization of the repeating unit.
  • the repeating unit having a graft chain can be formed by polymerizing a macromonomer.
  • the macromonomer means a polymer compound in which a polymerizable group is introduced at a polymer terminal.
  • the weight-average molecular weight of the macromonomer corresponds to the repeating unit having a graft chain.
  • the resin B may be a resin having a polymerizable group (hereinafter, also referred to as a polymerizable resin).
  • the polymerizable resin may be, for example, the above-described comb-shaped polymer or the above-described star polymer.
  • Examples of the polymerizable group include an ethylenically unsaturated bond-containing group, an epoxy group, a cyclic ether group such as an oxetane group, a methylol group, an alkoxymethyl group, and a blocked isocyanate group.
  • the amount of a polymerizable group-containing group in the polymerizable resin is preferably 0.01 to 5.0 mmol/g.
  • the upper limit is more preferably 4.0 mmol/g or less, still more preferably 3.0 mmol/g or less, even more preferably 2.0 mmol/g or less, and particularly preferably 1.5 mmol/g or less.
  • the lower limit is preferably 0.1 mmol/g or more and more preferably 0.2 mmol/g or more.
  • the amount of the polymerizable group in the polymerizable resin is a numerical value representing a molar amount of polymerizable group per 1 g of the solid content of the polymerizable resin.
  • a value calculated from the raw materials charged is used.
  • a value measured using a hydrolysis method is used.
  • a low-molecular-weight component (a) of polymerizable group site is extracted from the polymerizable resin by an alkali treatment, a content of the low-molecular-weight component is measured by high-performance liquid chromatography (HPLC), and the polymerizable group value in the polymerizable resin is calculated by the following expression.
  • HPLC high-performance liquid chromatography
  • NMR nuclear magnetic resonance
  • Polymerizable Group Value mmol / g of Polymerizable Resin Content ppm of Low-Molecular-Weight Component a / Molecular Weight g / mol of Low-Molecular-Weight Component a / Weighed Value g of Polymerizable Resin ⁇ Concentration of Solid Contents mass % of Polymerizable Resin / 100 ⁇ 10
  • polymerizable resin examples include a resin including a repeating unit having a polymerizable group in the side chain and a resin which is represented by Formula (SP-1) described above and has a structure in which at least one of Z 1 , A 1 , or P 1 is a polymerizable group.
  • SP-1 a resin which is represented by Formula (SP-1) described above and has a structure in which at least one of Z 1 , A 1 , or P 1 is a polymerizable group.
  • Examples of the repeating unit having a polymerizable group in the side chain include a repeating unit represented by Formula (A-1-1).
  • the resin including the repeating unit represented by Formula (A-1-1) may be used as a dispersant or a binder.
  • a content of the repeating unit having a polymerizable group is preferably 10 mol% or more, more preferably 10 to 80 mol%, and still more preferably 20 to 70 mol% with respect to the total repeating units of the polymerizable resin.
  • X 1 represents the main chain of the repeating unit
  • L 1 represents a single bond or a divalent linking group
  • Y 1 represents a polymerizable group.
  • the main chain of the repeating unit represented by X 1 is not particularly limited. It is not particularly limited as long as it is a linking group formed from a known polymerizable monomer. Examples thereof include a poly(meth)acrylic linking group, a polyalkyleneimine-based linking group, a polyester-based linking group, a polyurethane-based linking group, a polyuria-based linking group, a polyamide-based linking group, a polyether-based linking group, and a polystyrene-based linking group. Among these, a poly(meth)acrylic linking group or a polyalkyleneimine-based linking group is preferable, and a poly(meth)acrylic linking group is more preferable from the viewpoint of availability of raw materials and manufacturing suitability.
  • examples of the divalent linking group represented by L 1 include an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an alkyleneoxy group (preferably an alkyleneoxy group having 1 to 12 carbon atoms), an oxyalkylenecarbonyl group (preferably an oxyalkylenecarbonyl group having 1 to 12 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms), -NH-, -SO-, -SO 2 -, -CO-, -O-, -COO-, -OCO-, -S-, and a group formed by combination of two or more of these groups.
  • the alkylene group, the alkylene group in the alkyleneoxy group, and the alkylene group in the oxyalkylenecarbonyl group may be linear, branched, or cyclic, and are preferably linear or branched.
  • the alkylene group, the alkylene group in the alkyleneoxy group, and the alkylene group in the oxyalkylenecarbonyl group may have a substituent or may be unsubstituted. Examples of the substituent include a hydroxy group and an alkoxy group, and a hydroxy group is preferable from the viewpoint of manufacturing suitability.
  • examples of the polymerizable group represented by Y 1 include an ethylenically unsaturated bond-containing group and a cyclic ether group, and an ethylenically unsaturated bond-containing group is preferable.
  • examples of the ethylenically unsaturated bond-containing group include a vinyl group, a vinyloxy group, an allyl group, a methallyl group, a (meth)acryloyl group, a styrene group, a cinnamoyl group, and a maleimide group.
  • a (meth)acryloyl group, a styrene group, or a maleimide group is preferable, a (meth)acryloyl group is more preferable, and an acryloyl group is particularly preferable.
  • the resin including the repeating unit represented by Formula (A-1-1) may further include a repeating unit having a graft chain.
  • Examples of the repeating unit having a graft chain include the repeating unit represented by Formula (A-1-2) described above.
  • the content of the repeating unit having a graft chain is preferably 1.0 to 60 mol% and more preferably 1.5 to 50 mol% with respect to the total repeating units of the polymerizable resin.
  • the resin including the repeating unit represented by Formula (A-1-1) described above may further include a repeating unit having an acidic group.
  • a content of the repeating unit having an acidic group is preferably 80 mol% or less and more preferably 10 to 80 mol% with respect to the total repeating units of the polymerizable resin.
  • a commercially available product is also available as the resin B, and specific examples thereof include DISPERBYK series (for example, DISPERBYK-111, 2001, and the like) manufactured by BYK-Chemie Japan K.K., Solsperse series (for example, Solsperse 20000, 76500, and the like) manufactured by Lubrizol Corporation, and AJISPER series manufactured by Ajinomoto Fine-Techno Co., Inc.
  • DISPERBYK series for example, DISPERBYK-111, 2001, and the like
  • Solsperse series for example, Solsperse 20000, 76500, and the like
  • AJISPER series manufactured by Ajinomoto Fine-Techno Co., Inc.
  • products described in paragraph "0129" of JP2012-137564A and products described in paragraph "0235" of JP2017-194662A can also be used as the resin B.
  • a content of the resin B in the total solid content of the composition is preferably 0.1 to 60 mass%.
  • the lower limit is preferably 1 mass% or more and more preferably 5 mass% or more.
  • the upper limit is preferably 50 mass% or less, and more preferably 45 mass% or less.
  • the resin used in the composition preferably includes 10 mass% or more of the polymerizable resin (preferably, a resin including an ethylenically unsaturated bond-containing group), more preferably includes 20 mass% or more of the polymerizable resin, and still more preferably 30 mass% or more of the polymerizable resin with respect to the total mass of the resin.
  • the polymerizable resin preferably, a resin including an ethylenically unsaturated bond-containing group
  • the content of the resin used as a dispersant in the composition is preferably 5 to 150 parts by mass with respect to 100 parts by mass of the above-described white particles.
  • the upper limit is preferably 140 parts by mass or less, more preferably 125 parts by mass or less, and still more preferably 100 parts by mass or less.
  • the lower limit is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, and still more preferably 25 parts by mass or more.
  • the composition according to the embodiment of the present invention includes a resin having a polymerizable group and a resin not having a polymerizable group.
  • the phase separation is easily promoted due to polymerizable phase separation.
  • the content of the resin having a polymerizable group is preferably 5 to 90 parts by mass with respect to 100 parts by mass of the resin not having a polymerizable group.
  • the upper limit is preferably 85 parts by mass or less, more preferably 80 parts by mass or less, and still more preferably 70 parts by mass or less.
  • the lower limit is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, and still more preferably 25 parts by mass or more.
  • the polymerizable monomer a well-known compound which is crosslinkable by a radical, an acid, or heat can be used.
  • the polymerizable monomer include a compound having an ethylenically unsaturated bond-containing group and a compound having a cyclic ether group.
  • the ethylenically unsaturated bond-containing group include a vinyl group, a (meth)allyl group, and a (meth)acryloyl group.
  • the cyclic ether group include an epoxy group and an oxetanyl group.
  • a radically polymerizable monomer or a cationically polymerizable monomer is preferable, and a radically polymerizable monomer is more preferable.
  • the polymerizable monomer used in the present invention may be a polymerizable monomer including a ring structure, and in this case, a radically polymerizable monomer including a ring structure is more preferable.
  • a polymerizable monomer including a ring structure phase separation from the resin tends to occur.
  • the above-described effect is remarkable in a case of using a radically polymerizable monomer including a ring structure.
  • the ring structure included in the polymerizable monomer is preferably an aliphatic ring.
  • the aliphatic ring is preferably an aliphatic crosslinked ring.
  • the aliphatic crosslinked ring is an aliphatic ring having a structure in which two or more atoms that are not adjacent to each other are linked to one aliphatic ring.
  • Specific examples of the aliphatic crosslinked ring include a tricyclodecane ring and an adamantane ring, and a tricyclodecane ring is preferable.
  • the number of ring structures included in the polymerizable monomer is preferably 1 to 5, more preferably 1 to 3, and still more preferably 1.
  • Specific examples of the radically polymerizable monomer including a ring structure include dimethylol-tricyclodecanediacrylate and 1,3-adamantananediol diacrylate.
  • the radically polymerizable monomer is not particularly limited as long as it is a compound which is polymerizable by the action of a radical.
  • a compound having an ethylenically unsaturated bond-containing group is preferable, a compound having two or more ethylenically unsaturated bond-containing groups is more preferable, and a compound having three or more ethylenically unsaturated bond-containing groups is still more preferable.
  • the upper limit of the number of the ethylenically unsaturated bond-containing groups is, for example, preferably 15 or less and more preferably 6 or less.
  • Examples of the ethylenically unsaturated bond-containing group include a vinyl group, a styryl group (vinylphenyl group), a (meth)allyl group, and a (meth)acryloyl group. Among these, a (meth)acryloyl group is preferable.
  • the radically polymerizable monomer is preferably a (meth)acrylate compound having 3 to 15 functional groups and more preferably a (meth)acrylate compound having 3 to 6 functional groups.
  • the radically polymerizable monomer includes a ring structure.
  • a molecular weight of the radically polymerizable monomer is preferably 200 to 3,000.
  • the upper limit of the molecular weight is preferably 2,500 or less and still more preferably 2,000 or less.
  • the lower limit of the molecular weight is preferably 250 or more and still more preferably 300 or more.
  • the radically polymerizable monomer is a compound having a group having an ethylenically unsaturated bond-containing group which has a boiling point at 100°C or higher under normal pressure and has at least one ethylene group capable of addition polymerization.
  • Examples of the radically polymerizable monomer include: a monofunctional acrylate or methacrylate such as polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, or phenoxyethyl (meth)acrylate; polyethylene glycol di(meth)acrylate, trimethylol ethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hexanediol (meth)acrylate, trimethylol propane tri(acryloyloxypropyl)ether, or tri(acryloyloxyethyl)isocyanurate; and mixtures of the above-described compounds.
  • a compound represented by any one of the following Formulae (MO-1) to (MO-5) can also be suitably used.
  • T in the formulae represents an oxyalkylene group
  • a terminal thereof on a carbon atom side in T is bonded to R.
  • n 0 to 14
  • m 1 to 8.
  • a plurality of R's and a plurality of T's which are present in the same molecule may be the same as or different from each other.
  • Specific examples of the compounds represented by Formulae (MO-1) to (MO-5) include compounds described in paragraphs "0248" to "0251" of JP2007-269779A , the content of which is incorporated herein by reference.
  • dipentaerythritol triacrylate (as a commercially available product, KAYARAD D-330 manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercially available product, KAYARAD D-320 manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (as a commercially available product, KAYARAD D-310 manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (as a commercially available product, KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.
  • NK ESTER A-DPH-12E manufactured by Shin-Nakamura Chemical Co., Ltd. a compound having a structure in which a (meth)acryloyl group thereof is bonded through an ethylene glycol residue and/or a propylene glycol residue (for example, SR454 and SR499 available from Sartomer Japan Inc.), diglycerin ethylene oxide (EO)-modified (meth)acrylate (as a commercially available product, M-460 manufactured by TOAGOSEI CO., LTD.), pentaerythritol tetraacrylate (NK ESTER A-TMMT manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,6-hexanediol diacrylate (KAYARAD HDDA manufactured by Nippon Kayaku Co., Ltd.), KAYARAD RP-1040 (manufactured by Nippon Kayaku Co., Ltd.), ARONIX TO-2349 (manufactured by TOAGOSEI CO., LTD.
  • a trifunctional (meth)acrylate compound such as trimethylolpropane tri(meth)acrylate, trimethylolpropane propyleneoxide-modified tri(meth)acrylate, trimethylolpropane ethyleneoxide-modified tri(meth)acrylate, isocyanuric acid ethyleneoxide-modified tri(meth)acrylate, and pentaerythritol tri(meth)acrylate.
  • Examples of a commercially available product of the trifunctional (meth)acrylate compound include ARONIX M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306, M-305, M-303, M-452, and M-450 (manufactured by TOAGOSEI CO., LTD.), NK ESTER A9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A -TMM-3LM-N, A-TMPT, and TMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.), and KAYARAD GPO-303, TMPTA, THE-330, TPA-330, and PET-30 (manufactured by Nippon Kayaku Co., Ltd.).
  • the radically polymerizable monomer may have an acidic group such as a carboxy group, a sulfo group, or a phosphoric acid group.
  • Examples of the radically polymerizable monomer having an acidic group include an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid. Examples of a commercially available product include ARONIX series (for example, M-305, M-510, or M-520, manufactured by Toagosei Co., Ltd.).
  • An acid value of the radically polymerizable monomer having an acidic group is preferably 0.1 to 40 mgKOH/g.
  • the lower limit is preferably 5 mgKOH/g or more.
  • the upper limit is preferably 30 mgKOH/g or less.
  • Examples of the cationically polymerizable monomer include a compound having a cationically polymerizable group.
  • Examples of the cationically polymerizable group include a cyclic ether group such as an epoxy group or an oxetanyl group.
  • a compound having a cyclic ether group is preferable, and a compound having an epoxy group (also referred to as an "epoxy compound") is more preferable.
  • a molecular weight of the cationically polymerizable monomer is preferably 200 to 3,000.
  • the upper limit of the molecular weight is preferably 2,500 or less and still more preferably 2,000 or less.
  • the lower limit of the molecular weight is preferably 250 or more and still more preferably 300 or more.
  • Examples of the epoxy compound include a compound having one or more epoxy groups in one molecule. Among these, a compound having two or more epoxy groups in one molecule is preferable.
  • the number of epoxy groups in one molecule is preferably 1 to 100.
  • the upper limit of the epoxy group may be, for example, 10 or less or 5 or less.
  • the lower limit of the epoxy group is preferably 2 or more.
  • Examples of the epoxy compound include a compound represented by the following Formula (EP1).
  • R EP1 to R EP3 each independently represent a hydrogen atom, a halogen atom, or an alkyl group.
  • the alkyl group may have a cyclic structure or may have a substituent.
  • R EP1 and R EP2 , or R EP2 and R EP3 may be bonded to each other to form a ring structure.
  • Q EP represents a single bond or an n EP -valent organic group.
  • R EP1 to R EP3 may be bonded to Q EP to form a ring structure.
  • n EP represents an integer of 2 or more, preferably 2 to 10 and more preferably 2 to 6. However, in a case where Q EP is a single bond, n EP is 2.
  • R EP1 to R EP3 , and Q EP can be found in paragraphs "0087” and "0088” of JP2014-089408A , the content of which is incorporated herein by reference.
  • Specific examples of the compound represented by Formula (EP1) include a compound described in paragraph "0090” of JP2014-089408A and a compound described in paragraph "0151” of JP2010-054632A , the contents of which are incorporated herein by reference.
  • a commercially available product can also be used as the cationically polymerizable monomer.
  • the commercially available product include ADEKA GLYCILOL series manufactured by Adeka Corporation (for example, ADEKA GLYCILOL ED-505) and EPOLEAD series manufactured by Daicel Corporation (for example, EPOLEAD GT401).
  • the content of the polymerizable monomer in the total solid content of the composition is preferably 0.1 to 40 mass%.
  • the lower limit is preferably 0.5 mass% or more and more preferably 1 mass% or more.
  • the upper limit is preferably 30 mass% or less and more preferably 20 mass% or less.
  • the polymerizable monomer one kind may be used alone, or two or more kinds may be used in combination. In a case where two or more polymerizable monomers are used in combination, it is preferable that the total content of the two or more polymerizable monomers is within the above-described range.
  • two or more polymerizable monomers are used in combination
  • two or more radically polymerizable monomers may be used in combination
  • a radically polymerizable monomer and a cationically polymerizable monomer may be used in combination.
  • the total content of the polymerizable monomer and the resin in the total solid content of the composition is preferably 10 to 90 mass%.
  • the upper limit is preferably 80 mass% or less, and more preferably 75 mass% or less.
  • the lower limit is preferably 20 mass% or more and more preferably 30 mass% or more.
  • the ratio of the polymerizable monomer to the resin is preferably 10 to 400 parts by mass of the polymerizable monomer with respect to 100 parts by mass of the resin.
  • the lower limit is preferably 15 parts by mass or more and more preferably 20 parts by mass or more.
  • the upper limit is preferably 380 parts by mass or less and more preferably 350 parts by mass or less.
  • the composition according to the embodiment of the present invention includes a solvent.
  • the solvent include an organic solvent.
  • the solvent is not particularly limited as long as it satisfies the solubility of the respective components and the application properties of the composition.
  • the organic solvent include an ester solvent, a ketone solvent, an alcohol solvent, an amide solvent, an ether solvent, and a hydrocarbon solvent. The details of the organic solvent can be found in paragraph "0223" of WO2015/166779A , the content of which is incorporated herein by reference.
  • an ester solvent in which a cyclic alkyl group is substituted or a ketone solvent in which a cyclic alkyl group is substituted can also be preferably used.
  • organic solvent examples include acetone, methyl ethyl ketone, cyclohexane, cyclohexanone, cyclopentanone, ethyl acetate, butyl acetate, cyclohexyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetylacetone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diol
  • an organic solvent having a low metal content is preferably used.
  • the metal content in the organic solvent is preferably 10 mass parts per billion (ppb) or less.
  • an organic solvent having a metal content at a mass parts per trillion (ppt) level may be used.
  • such an organic solvent is available from Toyo Gosei Co., Ltd. (The Chemical Daily, November 13, 2015).
  • Examples of a method of removing impurities such as metal from the organic solvent include distillation (for example, molecular distillation or thin-film distillation) and filtering using a filter.
  • the pore size of a filter used for the filtering is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, and still more preferably 3 ⁇ m or less.
  • As a material of the filter polytetrafluoroethylene, polyethylene, or nylon is preferable.
  • the organic solvent may include an isomer (a compound having the same number of atoms and a different structure).
  • the organic solvent may include only one isomer or a plurality of isomers.
  • the organic solvent preferably has the content of peroxides of 0.8 mmol/L or less, and it is more preferable that the organic solvent does not substantially include peroxides.
  • An SP value of the solvent is preferably 17.00 to 24.00 MPa 0.5 , more preferably 18.00 to 22.00 MPa 0.5 , and still more preferably 18.50 to 20.00 MPa 0.5 .
  • Examples of the solvent having an SP value within the above-described range include propylene glycol monomethyl ether acetate (18.83), propylene glycol monomethyl ether (23.57), cyclohexanone (20.47), cyclopentanone (21.25), and butyl acetate (19.84).
  • the numerical values in parentheses represent the SP value of each solvent, respectively.
  • a difference between the SP value of the solvent and the SP value of the polymer structure included in the above-described constitutional unit A is preferably 0.00 to 1.23 MPa 0.5 , more preferably 0.00 to 0.82 MPa 0.5 , and still more preferably 0.00 to 0.41 MPa 0.5 .
  • the content of the solvent in the composition is preferably 10 to 95 mass%.
  • the lower limit is preferably 20 mass% or more, more preferably 30 mass% or more, and still more preferably 40 mass% or more.
  • the upper limit is preferably 90 mass%% or less, more preferably 85 mass% or less, and still more preferably 80 mass% or less.
  • the solvent one kind may be used alone, or two or more kinds may be used in combination. In a case where two or more solvents are used in combination, it is preferable that the total content of the solvents is within the above-described range.
  • the composition according to the embodiment of the present invention may contain a photopolymerization initiator.
  • the photopolymerization initiator include a photoradical polymerization initiator and a photocationic polymerization initiator. It is preferable that the photopolymerization initiator selected according to the type of the polymerizable monomer is used. In a case where a radically polymerizable monomer is used as the polymerizable monomer, it is preferable that the photoradical polymerization initiator is used as the photopolymerization initiator.
  • the photocationic polymerization initiator is used as the photopolymerization initiator.
  • the photopolymerization initiator is not particularly limited and can be appropriately selected from well-known photopolymerization initiators. For example, a compound having photosensitivity to light in a range from an ultraviolet range to a visible range is preferable.
  • the content of the photopolymerization initiator in the total solid content of the composition is preferably 0.1 to 50 mass%, more preferably 0.5 to 30 mass%, and still more preferably 1 to 20 mass%.
  • the composition according to the embodiment of the present invention may include one photopolymerization initiator or two or more photopolymerization initiators. In a case where the composition includes two or more photopolymerization initiators, it is preferable that the total content of the photopolymerization initiators is within the above-described range.
  • the photoradical polymerization initiator examples include a halogenated hydrocarbon derivative (for example, a compound having a triazine skeleton or a compound having an oxadiazole skeleton), an acylphosphine compound, a hexaarylbiimidazole, an oxime compound, an organic peroxide, a thio compound, a ketone compound, an aromatic onium salt, an ⁇ -hydroxyketone compound, and an ⁇ -aminoketone compound.
  • a halogenated hydrocarbon derivative for example, a compound having a triazine skeleton or a compound having an oxadiazole skeleton
  • an acylphosphine compound for example, a compound having a triazine skeleton or a compound having an oxadiazole skeleton
  • an acylphosphine compound for example, a compound having a triazine skeleton or a compound having an oxadiazole
  • a trihalomethyltriazine compound, a benzyldimethylketal compound, an ⁇ -hydroxyketone compound, an ⁇ -aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triarylimidazole dimer, an onium compound, a benzothiazole compound, a benzophenone compound, an acetophenone compound, a cyclopentadiene-benzene-iron complex, a halomethyl oxadiazole compound, or a 3-aryl-substituted coumarin compound is preferable, a compound selected from the group consisting of an oxime compound, an ⁇ -hydroxyketone compound, an ⁇ -aminoketone compound, and an acylphosphine compound is more preferable, and an oxime compound is still more preferable
  • Examples of a commercially available product of the ⁇ -hydroxyketone compound include Omnirad 184, Omnirad 1173, Omnirad 2959, and Omnirad 127 (all of which are manufactured by IGM Resins B.V.), Irgacure 184, Irgacure 1173, Irgacure 2959, and Irgacure 127 (all of which are manufactured by BASF).
  • Examples of a commercially available product of the ⁇ -aminoketone compound include Omnirad 907, Omnirad 369, Omnirad 369E, and Omnirad 379EG (all of which are manufactured by IGM Resins B.V.), Irgacure 907, Irgacure 369, Irgacure 369E, and Irgacure 379EG (all of which are manufactured by BASF).
  • Examples of a commercially available product of the acylphosphine compound include Omnirad 819 and Omnirad TPO (both of which are manufactured by IGM Resins B.V.), Irgacure 819 and Irgacure TPO (both of which are manufactured by BASF).
  • Examples of the oxime compound include the compounds described in JP2001-233842A , the compounds described in JP2000-080068A , the compounds described in JP2006-342166A , the compounds described in J. C. S. Perkin II (1979, pp. 1653 to 1660 ), the compounds described in J. C. S. Perkin II (1979, pp. 156 to 162 ), the compounds described in Journal of Photopolymer Science and Technology (1995, pp.
  • oxime compound examples include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluene sulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one.
  • Examples of a commercially available product thereof include Irgacure OXE01, Irgacure OXE02, Irgacure OXE03, and Irgacure OXE04 (all of which are manufactured by BASF), TR-PBG-304 (manufactured by TRONLY), and ADEKA OPTOMER N-1919 (manufactured by ADEKA Corporation; photopolymerization initiator 2 described in JP2012-014052A ).
  • the oxime compound it is also preferable to use a compound having no colorability or a compound having high transparency and being resistant to discoloration.
  • Examples of a commercially available product of the oxime compound include ADEKA ARKLS NCI-730, NCI-831, and NCI-930 (all of which are manufactured by Adeka Corporation).
  • An oxime compound having a fluorene ring can also be used as the photopolymerization initiator.
  • Specific examples of the oxime compound having a fluorene ring include a compound described in JP2014-137466A .
  • an oxime compound having a skeleton in which at least one benzene ring of a carbazole ring is a naphthalene ring can also be used.
  • Specific examples of such an oxime compound include the compounds described in WO2013/083505A .
  • An oxime compound having a fluorine atom can also be used as the photopolymerization initiator.
  • Specific examples of the oxime compound having a fluorine atom include a compound described in JP2010-262028A , Compound 24 and 36 to 40 described in JP2014-500852A , and Compound (C-3) described in JP2013-164471A .
  • An oxime compound having a nitro group can be used as the photopolymerization initiator. It is preferable that the oxime compound having a nitro group is a dimer. Specific examples of the oxime compound having a nitro group include a compound described in paragraphs "0031" to "0047" of JP2013-114249A and paragraphs "0008" to "0012” and “0070” to "0079” of JP2014-137466A , a compound described in paragraphs "0007” to 0025" of JP4223071B , and ADEKA ARKLS NCI-831 (manufactured by Adeka Corporation).
  • An oxime compound having a benzofuran skeleton can also be used as the photopolymerization initiator. Specific examples thereof include OE-01 to OE-75 described in WO2015/036910A .
  • oxime compound which are preferably used in the present invention are shown below, but the present invention is not limited thereto.
  • the oxime compound is preferably a compound having a maximal absorption wavelength in a wavelength in a range of 350 to 500 nm and more preferably a compound having a maximal absorption wavelength in a wavelength in a range of 360 to 480 nm.
  • the molar absorption coefficient of the oxime compound at a wavelength of 365 nm or 405 nm is preferably high, more preferably 1000 to 300000, still more preferably 2000 to 300000, and particularly preferably 5000 to 200000.
  • the molar absorption coefficient of the compound can be measured using a well-known method.
  • the molar absorption coefficient can be measured using a spectrophotometer (Cary-5 spectrophotometer, manufactured by Varian Medical Systems, Inc.) and ethyl acetate at a concentration of 0.01 g/L.
  • a spectrophotometer Carbon-5 spectrophotometer, manufactured by Varian Medical Systems, Inc.
  • ethyl acetate at a concentration of 0.01 g/L.
  • a bifunctional or tri- or higher functional photoradical polymerization initiator may be used as the photopolymerization initiator.
  • a photoradical polymerization initiator two or more radicals are generated from one molecule of the photoradical polymerization initiator, and as a result, good sensitivity is obtained.
  • crystallinity is reduced so that solubility in a solvent or the like is improved, precipitation is to be difficult over time, and temporal stability of the coloring composition can be improved.
  • bifunctional or tri- or higher functional photoradical polymerization initiator include dimers of the oxime compounds described in JP2010-527339A , JP2011-524436A , WO2015/004565A , paragraphs "0407” to "0412” of JP2016-532675A , and paragraphs "0039” to "0055” of WO2017/033680A ; the compound (E) and compound (G) described in JP2013-522445A ; Cmpd 1 to 7 described in WO2016/034963A ; the oxime ester photoinitiators described in paragraph "0007" of JP2017-523465A ; the photoinitiators described in paragraphs "0020” to "0033” of JP2017-167399A ; and the photopolymerization initiator (A) described in paragraphs "0017” to "0026” of JP2017-151342A .
  • the content of the photoradical polymerization initiator in the total solid content of the composition is preferably 0.1 to 50 mass%, more preferably 0.5 to 30 mass%, and still more preferably 1 to 20 mass%.
  • the composition according to the embodiment of the present invention may include one photoradical polymerization initiator or two or more photoradical polymerization initiators. In a case where the composition includes two or more photoradical polymerization initiators, it is preferable that the total content of the photoradical polymerization initiators is within the above-described range.
  • Examples of the photocationic polymerization initiator include a photoacid generator.
  • Examples of the photoacid generator include compounds which are decomposed by light irradiation to generate an acid including: an onium salt compound such as a diazonium salt, a phosphonium salt, a sulfonium salt, or an iodonium salt; and a sulfonate compound such as imidosulfonate, oximesulfonate, diazodisulfone, disulfone, or o-nitrobenzyl sulfonate.
  • an onium salt compound such as a diazonium salt, a phosphonium salt, a sulfonium salt, or an iodonium salt
  • a sulfonate compound such as imidosulfonate, oximesulfonate, diazodisulfone, disulfone, or o-nitrobenzyl sulfonate.
  • photocationic polymerization initiator examples include compounds represented by the following Formulae (b1), (b2), and (b3).
  • R 201 to R 207 each independently represent an organic group.
  • the number of carbon atoms in the organic group is preferably 1 to 30.
  • Examples of the organic group include an alkyl group and an aryl group.
  • two of R 201 to R 203 may be bonded to each other to form a ring structure, and the ring may include an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group.
  • X - represents a non-nucleophilic anion.
  • non-nucleophilic anion examples include a sulfonate anion, a carboxylate anion, a bis(alkylsulfonyl)amide anion, a tris(alkylsulfonyl)methide anion, BF 4 - , PF 6 - , and SbF 6 - .
  • the details of the compound represented by Formulae (b1), (b2), and (b3) can be found in paragraphs "0139" to "0214" of JP2009-258603A , the content of which is incorporated herein by reference.
  • photocationic polymerization initiator examples include a compound having the following structure.
  • the photocationic polymerization initiator a commercially available product can also be used.
  • the commercially available product of the photocationic polymerization initiator include ADEKA ARKLS SP series manufactured by Adeka Corporation (for example, ADEKA ARKLS SP-606) and IRGACURE 250, IRGACURE 270, and IRGACURE 290 manufactured by BASF.
  • the content of the photocationic polymerization initiator in the total solid content of the composition is preferably 0.1 to 50 mass%, more preferably 0.5 to 30 mass%, and still more preferably 1 to 20 mass%.
  • the composition according to the embodiment of the present invention may include one photocationic polymerization initiator or two or more photocationic polymerization initiators. In a case where the composition includes two or more photocationic polymerization initiators, it is preferable that the total content of the two or more photocationic polymerization initiators is within the above-described range.
  • the composition according to the embodiment of the present invention may further contain a pigment derivative.
  • the pigment derivative include a compound having a structure in which a portion of a chromophore is substituted with an acidic group, a basic group, or a phthalimidomethyl group.
  • the acidic group include a sulfo group, a carboxy group, and a quaternary ammonium salt group thereof.
  • the basic group include an amino group.
  • the content of the pigment derivative is preferably 1 to 30 parts by mass and more preferably 3 to 20 parts by mass with respect to 100 parts by mass of the pigment.
  • these pigment derivatives one kind may be used alone, or two or more kinds may be used in combination. In a case where two or more pigment derivatives are used in combination, it is preferable that the total content of the pigment derivatives is within the above-described range.
  • the composition according to the embodiment of the present invention may contain an anti-coloring agent.
  • the anti-coloring agent described in this specification may be used as a polymerization inhibitor.
  • the anti-coloring agent include a phenol compound, a phosphite compound, and a thioether compound.
  • a phenol compound having a molecular weight of 500 or more, a phosphite compound having a molecular weight of 500 or more, or a thioether compound having a molecular weight of 500 or more is more preferable.
  • a phenol compound is preferable, and a phenol compound having a molecular weight of 500 or more is more preferable.
  • any phenol compound which is known as a phenol anti-coloring agent can be used.
  • a hindered phenol compound is preferable.
  • a compound having a substituent at a position (ortho position) adjacent to a phenolic hydroxy group is preferable.
  • a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable.
  • a compound having a phenol group and a phosphite group in the same molecule is also preferable.
  • a polysubstituted phenol compound is suitably used as the phenolic hydroxy group-containing compound.
  • the polysubstituted phenol compound can be classified into three types (a hindered type represented by the following Formula (A), a semi-hindered type represented by the following Formula (B), and a less-hindered type represented by the following Formula (C)) having different substitution sites and different structures in terms of reactivity to a peroxy radical trapped for the stable generation of a phenoxy radical.
  • R represents a hydrogen atom or a substituent.
  • R represents preferably a hydrogen atom, a halogen atom, an amino group which may have a substituent, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylamino group which may have a substituent, an arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, or an arylsulfonyl group which may have a substituent, and more preferably an amino group which may have a substituent, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylamino group which may have a substituent.
  • a composite anti-coloring agent in which a plurality of structures represented by Formulae (A) to (C) having an anti-coloring function are present in the same molecule is still more preferable.
  • a compound in which 2 to 4 structures represented by Formulae (A) to (C) having an anti-coloring function are present in the same molecule is preferable.
  • the semi-hindered type represented by Formula (B) is more preferable from the viewpoint of colorability.
  • Representative examples of a commercially available product of (A) include SUMILIZER BHT (manufactured by Sumitomo Chemical Co., Ltd.), IRGANOX 1010 and 1222 (manufactured by BASF), and ADEKA STAB AO-20, AO-50, and AO-60 (manufactured by Adeka Corporation).
  • Representative examples of a commercially available product of (B) include SUMILIZER BBM-S (manufactured by Sumitomo Chemical Co., Ltd.), IRGANOX 245 (manufactured by BASF), and ADEKA STAB AO-80 (manufactured by Adeka Corporation).
  • Representative examples of a commercially available product of (C) include ADEKA STAB AO-30 and AO-40 (manufactured by Adeka Corporation).
  • Examples of the phosphite compound and the thioether compound include compounds described in paragraphs 0213 and 0214 of WO2017/159910A and commercially available products.
  • examples of a commercially available product of the anti-coloring agent include ADEKA STAB AO-50F, ADEKA STAB AO-60G, and ADEKA STAB AO-330 (manufactured by Adeka Corporation).
  • anti-coloring agent examples include:
  • the content of the anti-coloring agent in the total solid content of the composition is preferably 0.01 to 20 mass%, more preferably 0.1 to 15 mass%, and still more preferably 0.3 to 5 mass%.
  • the anti-coloring agent one kind may be used alone, or two or more kinds may be used in combination. In a case where two or more kinds thereof are used in combination, it is preferable that the total content of the two or more kinds thereof is within the above-described range.
  • the composition according to the embodiment of the present invention may contain an ultraviolet absorber.
  • the ultraviolet absorber include a conjugated diene compound, an aminobutadiene compound, a methyldibenzoyl compound, a coumarin compound, a salicylate compound, a benzophenone compound, a benzotriazole compound, an acrylonitrile compound, and a hydroxyphenyltriazine compound.
  • the details of the ultraviolet absorber can be found in paragraphs "0052" to "0072" of JP2012-208374A and paragraphs "0317” to "0334" of JP2013-068814A , the contents of which are incorporated herein by reference.
  • Examples of a commercially available product of the conjugated diene compound include UV-503 (manufactured by Daito Chemical Co., Ltd.).
  • MYUA series manufactured by Miyoshi Oil&Fat Co., Ltd.; The Chemical Daily, February 1, 2016
  • Miyoshi Oil&Fat Co., Ltd. The Chemical Daily, February 1, 2016
  • the content of the ultraviolet absorber in the total solid content of the composition is preferably 0.1 to 10 mass%, more preferably 0.1 to 7 mass%, still more preferably 0.1 to 5 mass%, and still more preferably 0.1 to 3 mass%.
  • the ultraviolet absorber one kind may be used alone, or two or more kinds may be used in combination. In a case where two or more kinds thereof are used in combination, it is preferable that the total content of the two or more kinds thereof is within the above-described range.
  • composition according to the embodiment of the present invention may contain an adhesive.
  • adhesive well-known adhesives can be used without any particular limitation.
  • examples of the adhesive include a silane coupling agent.
  • the silane coupling agent refers to a silane compound having a functional group other than a hydrolyzable group.
  • the hydrolyzable group refers to a substituent directly linked to a silicon atom and capable of forming a siloxane bond due to at least one of a hydrolysis reaction or a condensation reaction.
  • the hydrolyzable group include a halogen atom, an alkoxy group, and an acyloxy group. Among these, an alkoxy group is preferable. That is, it is preferable that the silane coupling agent is a compound having an alkoxysilyl group.
  • Examples of the functional group other than a hydrolyzable group include a vinyl group, a (meth)allyl group, a (meth)acryloyl group, a mercapto group, an epoxy group, an oxetanyl group, an amino group, an ureide group, a sulfide group, an isocyanate group, and a phenyl group.
  • an amino group, a (meth)acryloyl group, or an epoxy group is preferable.
  • silane coupling agent examples include N- ⁇ -aminoethyl- ⁇ -aminopropyl methyldimethoxysilane (trade name: KBM-602, manufactured by Shin-Etsu Chemical Co., Ltd.), N- ⁇ -aminoethyl- ⁇ -aminopropyl trimethoxysilane (trade name: KBM-603, manufactured by Shin-Etsu Chemical Co., Ltd.), N- ⁇ -aminoethyl- ⁇ -aminopropyl triethoxysilane (trade name: KBE-602, manufactured by Shin-Etsu Chemical Co., Ltd.), ⁇ -aminopropyl trimethoxysilane (trade name: KBM-903, manufactured by Shin-Etsu Chemical Co., Ltd.), ⁇ -aminopropyl triethoxysilane (trade name: KBE-903, manufactured by Shin-Etsu Chemical Co., Ltd.), 3-methacryloxypropyl methyldimethoxys
  • silane coupling agent examples include a compound described in paragraphs "0018" to “0036” of JP2009-288703A and a compound described in paragraphs "0056” to “0066” of JP2009-242604A , the contents of which are incorporated herein by reference.
  • the content of the adhesive in the total solid content of the composition is preferably 0.01 to 10 mass%, more preferably 0.1 to 7 mass%, and still more preferably 1 to 5 mass%.
  • the adhesive one kind may be used alone, or two or more kinds may be used in combination. In a case where two or more kinds thereof are used in combination, it is preferable that the total content of the two or more kinds thereof is within the above-described range.
  • the composition according to the embodiment of the present invention may contain a polymerization inhibitor.
  • the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butyl catechol, 1,4-benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), and an N-nitrosophenylhydroxylamine salt (an ammonium salt, a cerous salt, or the like).
  • p-methoxyphenol is preferable.
  • the content of the polymerization inhibitor in the total solid content of the composition is preferably 0.0001 to 5 mass%.
  • composition according to the embodiment of the present invention may contain a chain transfer agent.
  • a chain transfer agent the compound described in paragraph 0225 of WO2017/159190A can be used.
  • the content of the chain transfer agent in the total solid content of the composition is preferably 0.2 to 5.0 mass% and more preferably 0.4 to 3.0 mass%.
  • the content of the chain transfer agent is preferably 1 to 40 parts by mass, and more preferably 2 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer.
  • the chain transfer agent one kind may be used alone, or two or more kinds may be used in combination. In a case where two or more kinds thereof are used in combination, it is preferable that the total content of the two or more kinds thereof is within the above-described range.
  • the composition according to the embodiment of the present invention may contain a sensitizer in order to improve the radical generation efficiency of the photopolymerization initiator and to increase a photosensitive wavelength. It is preferable that the sensitizer sensitizes the photopolymerization initiator using an electron migration mechanism or an energy-transfer mechanism. Examples of the sensitizer include a compound having an absorption in a wavelength in a range of 300 to 450 nm. With regard to the sensitizer, the details can be found in the description of paragraphs "0231" to "0253” of JP2010-106268A (corresponding to paragraphs "0256” to "0273” of US2011/0124824A ), the content of which is incorporated herein by reference.
  • the content of the sensitizer in the total solid content of the composition is preferably 0.1 to 20 mass% and more preferably 0.5 to 15 mass%.
  • the sensitizer one kind may be used alone, or two or more kinds may be used in combination. In a case where two or more kinds thereof are used in combination, it is preferable that the total content of the two or more kinds thereof is within the above-described range.
  • the composition according to the embodiment of the present invention further contains a co-sensitizer.
  • the co-sensitizer has a function of further improving sensitivity of the photopolymerization initiator or the sensitizer to radioactive ray, or of suppressing inhibition of polymerization of the polymerizable monomer due to oxygen.
  • the details can be found in the description of paragraphs "0254" to "0257” of JP2010-106268A (corresponding to paragraphs "0277” to "0279” of US2011/0124824A ), the content of which is incorporated herein by reference.
  • the content of the co-sensitizer in the total solid content of the composition is preferably 0.1 to 30 mass%, more preferably 1 to 25 mass%, and still more preferably 1.5 to 20 mass%.
  • the co-sensitizer one kind may be used alone, or two or more kinds may be used in combination. In a case where two or more kinds thereof are used in combination, it is preferable that the total content of the two or more kinds thereof is within the above-described range.
  • composition according to the embodiment of the present invention may contain various surfactants from the viewpoint of further improving suitability for application.
  • various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, or a silicone-based surfactant can be used.
  • compositions according to the embodiment of the present invention containing a fluorine-based surfactant liquid characteristics (for example, fluidity) of a coating liquid prepared from the coloring composition are further improved, and the uniformity in coating thickness and liquid saving properties can be further improved. That is, in a case where a film is formed of a coating liquid prepared using the composition including a fluorine-based surfactant, the interfacial tension between a coated surface and the coating liquid decreases, the wettability on the coated surface is improved, and the suitability for application on the coated surface is improved. Therefore, a film having a uniform thickness with reduced unevenness in thickness can be formed more suitably.
  • a fluorine-based surfactant liquid characteristics (for example, fluidity) of a coating liquid prepared from the coloring composition are further improved, and the uniformity in coating thickness and liquid saving properties can be further improved. That is, in a case where a film is formed of a coating liquid prepared using the composition including a fluorine-based surfactant, the interfacial tension between a
  • the fluorine content in the fluorine-based surfactant is preferably 3 to 40 mass%, more preferably 5 to 30 mass%, and still more preferably 7 to 25 mass%.
  • the fluorine-based surfactant in which the fluorine content is in the above-described range is effective from the viewpoints of the uniformity in the thickness of the coating film and liquid saving properties, and the solubility thereof in the composition is also excellent.
  • fluorine-based surfactant examples include a surfactant described in paragraphs "0060” to “0064” of JP2014-041318A (paragraphs “0060” to “0064” of corresponding WO2014/017669A ) and a surfactant described in paragraphs "0117” to "0132” of JP2011-132503A , the contents of which are incorporated herein by reference.
  • Examples of a commercially available product of the fluorine-based surfactant include: MEGAFACE F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, EXP, and MFS-330 (all of which are manufactured by DIC Corporation); FLUORAD FC430, FC431, and FC171 (all of which are manufactured by Sumitomo 3M Ltd.); SURFLON S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, and KH-40 (all of which are manufactured by Asahi Glass Co., Ltd.); POLYFOX PF636, PF656, PF6320, PF6520, and PF7002 (all of which are manufactured by OMNOVA Solutions Inc.); and FTERGENT FTX218 (manufactured by NEOS COMPANY LIMITED).
  • an acrylic compound in which, in a case where heat is applied to a molecular structure which has a functional group having a fluorine atom, the functional group having a fluorine atom is cut and a fluorine atom is volatilized can also be suitably used.
  • a fluorine-based surfactant include MEGAFACE DS series manufactured by DIC Corporation (The Chemical Daily (February 22, 2016) and Nikkei Business Daily (February 23, 2016)), for example, MEGAFACE DS-21.
  • fluorine-based surfactant a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group, and a hydrophilic vinyl ether compound can be preferably used.
  • fluorine-based surfactant include fluorine-based surfactants described in JP2016-216602A , the contents of which are incorporated herein by reference.
  • a block polymer can also be used.
  • a fluorine-based surfactant a fluorine-containing polymer compound can be preferably used, the fluorine-containing polymer compound including: a repeating unit derived from a (meth)acrylate compound having a fluorine atom; and a repeating unit derived from a (meth)acrylate compound having 2 or more (preferably 5 or more) alkyleneoxy groups (preferably an ethyleneoxy group and a propyleneoxy group).
  • fluorine-containing surfactants described in paragraph "0016" to "0037" of JP2010-032698A or the following compounds are also exemplified as the fluorine-based surfactant used in the present invention.
  • a weight-average molecular weight of the above-described compounds is preferably 3,000 to 50,000, and is, for example, 14,000.
  • "%" representing the proportion of a repeating unit is mol%.
  • a fluorine-based surfactant a fluorine-containing polymer having an ethylenically unsaturated bond-containing group at a side chain can also be used.
  • Specific examples include a compound described in paragraphs "0050” to "0090” and paragraphs "0289” to "0295” of JP2010-164965A , for example, MEGAFACE RS-101, RS-102, RS-718K, and RS-72-K manufactured by DIC Corporation.
  • a compound described in paragraphs "0015" to "0158" of JP2015-117327A can also be used.
  • silicone-based surfactant examples include compounds described in paragraph 0243 of WO2017/159190A .
  • the content of the surfactant in the total solid content of the composition is preferably 0.001 to 2.0 mass% and more preferably 0.005 to 1.0 mass%.
  • the surfactant one kind may be used alone, or two or more kinds may be used in combination. In a case where two or more kinds thereof are used in combination, it is preferable that the total content of the two or more kinds thereof is within the above-described range.
  • a well-known additive such as a plasticizer or a sensitization agent may be added to the composition in order to improve physical properties of the film.
  • the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, and triacetyl glycerin.
  • a content of the plasticizer is preferably 10 mass% or less with respect to the total mass of all resins and polymerizable monomers included in the composition.
  • a storage container of the composition according to the embodiment of the present invention is not particularly limited, and a well-known storage container can be used.
  • a storage container in order to suppress infiltration of impurities into the raw materials or the composition, a multilayer bottle in which a container interior wall having a six-layer structure is formed of six kinds of resins or a bottle in which a container interior wall having a seven-layer structure is formed of six kinds of resins is preferably used.
  • the container include a container described in JP2015-123351A .
  • the container interior wall is formed of glass, stainless steel, or the like.
  • composition according to the embodiment of the present invention can be prepared by mixing the above-described components with each other.
  • the respective components may be mixed with each other collectively, or may be mixed with each other sequentially after at least dissolved or dispersed in a solvent.
  • the order of addition or working conditions are not particularly limited.
  • a process of dispersing the particles is provided in order to prepare the composition.
  • a mechanical force used for dispersing the particles in the process of dispersing the particles include compression, squeezing, impact, shearing, and cavitation.
  • Specific examples of the process include a beads mill, a sand mill, a roll mill, a ball mill, a paint shaker, a Microfluidizer, a high-speed impeller, a sand grinder, a project mixer, high-pressure wet atomization, and ultrasonic dispersion.
  • the process is performed under conditions for increasing the pulverization efficiency, for example, by using beads having a small size and increasing the filling rate of the beads.
  • rough particles are removed by filtering, centrifugal separation, and the like after pulverization.
  • the particles may be miniaturized in a salt milling step.
  • a material, a device, process conditions, and the like used in the salt milling step can be found in, for example, JP2015-194521A and JP2012-046629A .
  • the composition is filtered through a filter, for example, in order to remove foreign matter or to reduce defects.
  • a filter any filter which is used in the related art for filtering or the like can be used without any particular limitation.
  • a material of the filter include: a fluororesin such as polytetrafluoroethylene (PTFE); a polyamide resin such as nylon (for example, nylon-6 or nylon-6,6); and a polyolefin resin (including a polyolefin resin having a high density and an ultrahigh molecular weight) such as polyethylene or polypropylene (PP).
  • a fluororesin such as polytetrafluoroethylene (PTFE)
  • a polyamide resin such as nylon (for example, nylon-6 or nylon-6,6)
  • a polyolefin resin including a polyolefin resin having a high density and an ultrahigh molecular weight
  • polyethylene or polypropylene (PP) polypropylene
  • polypropylene including high-density polypropylene
  • the pore size of the filter is preferably 0.01 to 10.0 ⁇ m, more preferably 0.05 to 3.0 ⁇ m, and still more preferably about 0.1 to 2.0 ⁇ m.
  • the pore size value of the filter reference can be made to a nominal value of filter manufacturers.
  • various filters provided by Nihon Pall Corporation (DFA4201NIEY and the like), Advantec Toyo Kaisha., Ltd., Nihon Entegris G.K. (formerly Nippon Microlith Co., Ltd.), Kitz Microfilter Corporation, and the like can be used.
  • a fibrous filter material is used as the filter.
  • the fibrous filter material include polypropylene fiber, nylon fiber, and glass fiber.
  • examples of a commercially available product include SBP type series (SBP008 and the like), TPR type series (TPR002, TPR005, and the like), or SHPX type series (SHPX003 and the like), all manufactured by Roki Techno Co., Ltd.
  • a combination of different filters for example, a first filter and a second filter
  • the filtering using each of the filters may be performed once, or twice or more.
  • a combination of filters having different pore sizes in the above-described range may be used.
  • the filtering using the first filter may be performed only on the dispersion liquid
  • the filtering using the second filter may be performed on a mixture of the dispersion liquid and other components.
  • a first aspect of the film according to the embodiment of the present invention is a film consisting of the composition according to the embodiment of the present invention.
  • the maximum value of the transmittance of the film to light having a wavelength in a range of 400 to 700 nm is preferably 80% or less, more preferably 70% or less, still more preferably 60% or less, and particularly preferably 50% or less.
  • the lower limit of the above-described maximum value of the light transmittance is preferably 1% or more, more preferably 5% or more, and still more preferably 10% or more.
  • a second aspect of the film according to the embodiment of the present invention is a film including white particles having a refractive index of 2.0 or more and an average primary particle diameter of 200 nm or less and a film-forming component including at least one selected from a resin and a polymerizable monomer or a cured substance of the film-forming component, in which the film-forming component includes two or more kinds of resins, or includes one or more kinds of resins and one or more kinds of polymerizable monomers, at least one of the resin is a resin A which contains a constitutional unit A having a formula weight of 1,000 or more and including a constitutional unit GF and a constitutional unit B having an acidic group, and satisfies at least one of the above-described requirement 1 or requirement 2, and the constitutional unit GF is selected from the group consisting of a constitutional unit represented by Formula (1-1) described above and a constitutional unit represented by Formula (1-2) described above.
  • the materials described in the above-described sections of the composition according to the embodiment of the present invention can be mentioned, and preferred ranges thereof are also the same.
  • the film of the second aspect may further include a material other than the particles and the film-forming component included in the above-described composition according to the embodiment of the present invention. Preferred aspects of these materials are as described above.
  • a phase-separated structure between a first phase including the above-described white particles and a second phase with a lower content of the above-described white particles than the first phase is formed in the above-described film.
  • the above-described phase-separated structure is preferably a sea-island structure or a co-continuous phase structure.
  • the second phase may form the sea and the first phase may form the island, or the first phase may form the sea and the second phase may form the island.
  • the case where the first phase forms the sea and the second phase forms the island is preferable from the viewpoint of transmittance.
  • the case where the first phase forms the island and the second phase forms the sea is preferable from the viewpoint of angle dependence.
  • the maximum value of the transmittance of the film to light having a wavelength in a range of 400 to 700 nm is preferably 80% or less, more preferably 70% or less, still more preferably 60% or less, and particularly preferably 50% or less.
  • the lower limit of the above-described maximum value of the light transmittance is preferably 1% or more, more preferably 5% or more, and still more preferably 10% or more.
  • the maximum value of the transmittance of the film to light at 400 to 1000 nm is preferably 80% or less, more preferably 60% or less, and still more preferably 50% or less.
  • the lower limit of the above-described maximum value of the light transmittance is preferably 1% or more, more preferably 5% or more, and still more preferably 10% or more.
  • the haze of the film according to the embodiment of the present invention based on JIS K 7136 is preferably 30% to 100%.
  • the upper limit is preferably 99% or less, more preferably 95% or less, and still more preferably 90% or less.
  • the lower limit is preferably 35% or more, more preferably 40% or more, and still more preferably 50% or more.
  • the haze of the film is a value measured according to the method in Examples described later.
  • the value of L ⁇ of the film according to the embodiment of the present invention in the L*a*b* color system of CIE 1976 is preferably 35 to 100.
  • the value of L ⁇ is preferably 40 or more, more preferably 50 or more, and still more preferably 60 or more. According to this aspect, a film having excellent whiteness can be formed.
  • the value of L ⁇ is preferably 95 or less, more preferably 90 or less, and still more preferably 85 or less. According to this aspect, a film having appropriate visible light transparency can be formed.
  • the value of a* is preferably -15 or more, more preferably -10 or more, and still more preferably -5 or more.
  • the value of a* is preferably 10 or less, more preferably 5 or less, and still more preferably 0 or less. According to this aspect, a film having excellent whiteness can be formed.
  • the value of b ⁇ is preferably -35 or more, more preferably -30 or more, and still more preferably -25 or more.
  • the value of b* is preferably 20 or less, more preferably 10 or less, and still more preferably 0 or less. According to this aspect, a film having excellent whiteness can be formed.
  • the thickness of the film according to the embodiment of the present invention is preferably 2 to 40 ⁇ m.
  • the upper limit of the film thickness is preferably 30 ⁇ m or less, more preferably 20 ⁇ m or less, and still more preferably 15 ⁇ m or less.
  • the lower limit of the film thickness is preferably 3 ⁇ m or more, more preferably 4 ⁇ m or more, and still more preferably 5 ⁇ m or more. In a case where the film thickness is within the above-described range, an effect of improving a device optical sensitivity by reducing the thickness of a sensor and suppressing crosstalk can be expected.
  • the film according to the embodiment of the present invention can be formed through a step of applying the composition according to the embodiment of the present invention to a support.
  • the support include a substrate formed of a material such as silicon, non-alkali glass, soda glass, PYREX (registered trade name) glass, or quartz glass.
  • an organic film or an inorganic film may be formed on the substrate.
  • a material of the organic film include a resin.
  • a substrate formed of the resin can also be used as the support.
  • a charge coupled device (CCD), a complementary metal-oxide semiconductor (CMOS), a transparent conductive film, or the like may be formed on the support.
  • a black matrix that separates pixels from each other may be formed on the support.
  • an undercoat layer may be provided on the support to improve adhesiveness with a layer above the support, to prevent diffusion of materials, or to make a surface of the substrate flat.
  • an inorganic film is formed on the glass substrate or the glass substrate may be dealkalized to be used.
  • a well-known method can be used as a method of applying the composition to the support.
  • the well-known method include: a drop casting method; a slit coating method; a spray coating method; a roll coating method; a spin coating method; a cast coating method; a slit and spin method; a pre-wetting method (for example, a method described in JP2009-145395A ); various printing methods including jet printing such as an ink jet method (for example, an on-demand method, a piezoelectric method, or a thermal method) or a nozzle jet method, flexographic printing, screen printing, gravure printing, reverse offset printing, and metal mask printing; a transfer method using a mold or the like; and a nanoimprinting method.
  • jet printing such as an ink jet method (for example, an on-demand method, a piezoelectric method, or a thermal method) or a nozzle jet method, flexographic printing, screen printing, gravure printing, reverse offset printing, and metal mask printing;
  • the application method using an ink jet method is not particularly limited, and examples thereof include a method (in particular, pp. 115 to 133) described in "Extension of Use of Ink Jet - Infinite Possibilities in Patent-" (February, 2005, S.B. Research Co., Ltd.) and methods described in JP2003-262716A , JP2003-185831A , JP2003-261827A , JP2012-126830A , and JP2006-169325A .
  • the application using a spin coating method is preferably spin coating at 300 to 6000 rpm and more preferably spin coating at 400 to 3000 rpm.
  • the temperature of the support during spin coating is preferably 10°C to 100°C and more preferably 20°C to 70°C. In a case where the temperature of the support is in the above-described range, a film having excellent application uniformity is likely to be formed. In a case where the drop casting method is used, it is preferable that a drop range of the composition in which a photoresist is used as a partition wall is formed on the support such that a film having a predetermined uniform film thickness can be obtained. A desired film thickness can be obtained by controlling the drop amount and concentration of solid contents of the composition and the area of the drop range.
  • composition layer formed on the support may be dried (pre-baked).
  • pre-baking conditions of a temperature of 60°C to 150°C and 30 seconds to 15 minutes.
  • the method of forming the film according to the embodiment of the present invention may further include a step of forming a pattern.
  • a pattern forming method include a pattern forming method using a photolithography method and a pattern forming method using a dry etching method.
  • the step of forming a pattern is not necessarily performed.
  • the step of forming a pattern will be described in detail.
  • the pattern forming method using a photolithography method includes: a step (exposure step) of exposing the composition layer, which is formed by applying the composition according to the embodiment of the present invention, in a patterned manner; and a step (development step) of forming a pattern by removing a non-exposed portion of the composition layer for development.
  • the pattern forming method may further include a step (post-baking step) of baking the developed pattern.
  • the composition layer is exposed in a patterned manner.
  • the composition layer can be exposed in a pattern shape using an exposure device such as a stepper through a mask having a predetermined mask pattern.
  • an exposed portion can be cured.
  • the radiation (light) which can be used during the exposure include g-rays and i-rays.
  • light preferably light having a wavelength of 180 to 300 nm having a wavelength of 300 nm or less can also be used.
  • Examples of the light having a wavelength of 300 nm or less include KrF-rays (wavelength: 248 nm) and ArF-rays (wavelength: 193 nm), and KrF-rays (wavelength: 248 nm) are preferable.
  • the pulse exposure refers to an exposing method in which light irradiation and resting are repeatedly performed in a short cycle (for example, millisecond-level or less).
  • the pulse width is preferably 100 nanoseconds (ns) or less, more preferably 50 nanoseconds or less, and still more preferably 30 nanoseconds or less.
  • the lower limit of the pulse width is not particularly limited, and may be 1 femtosecond (fs) or more or 10 femtoseconds or more.
  • the frequency is preferably 1 kHz or more, more preferably 2 kHz or more, and still more preferably 4 kHz or more.
  • the upper limit of the frequency is preferably 50 kHz or less, more preferably 20 kHz or less, and still more preferably 10 kHz or less.
  • the maximum instantaneous illuminance is preferably 50,000,000 W/m 2 or more, more preferably 100,000,000 W/m 2 or more, and still more preferably 200,000,000 W/m 2 or more.
  • the upper limit of the maximum instantaneous illuminance is preferably 1,000,000,000 W/m 2 or less, more preferably 800,000,000 W/m 2 or less, and still more preferably 500,000,000 W/m 2 or less.
  • the pulse width refers to a time during which light is irradiated in a pulse period.
  • the frequency is the number of pulse periods per second.
  • the maximum instantaneous illuminance is average illuminance within the time during which light is radiated in the pulse period.
  • the pulse period is a period in which irradiation with light and resting are one cycle in the pulse exposure.
  • the irradiation amount is preferably 0.03 to 2.5 J/cm 2 , more preferably 0.05 to 1.0 J/cm 2 , and most preferably 0.08 to 0.5 J/cm 2 .
  • the oxygen concentration in a case of the exposure can be appropriately selected.
  • the exposure may be performed in air, in a low-oxygen atmosphere having an oxygen concentration of 19 vol% or less (for example, 15 vol%, 5 vol%, or substantially oxygen-free), or in a high-oxygen atmosphere having an oxygen concentration of more than 21 vol% (for example, 22 vol%, 30 vol%, or 50 vol%).
  • the exposure illuminance can be appropriately set, and is preferably selected in a range of 1000 to 100,000 W/m 2 .
  • Conditions of the oxygen concentration and conditions of the exposure illuminance may be appropriately combined. For example, conditions are oxygen concentration: 10 vol% and illuminance: 10,000 W/m 2 , or oxygen concentration: 35 vol% and illuminance: 20,000 W/m 2 .
  • a pattern is formed by removing a non-exposed portion of the exposed composition layer by development.
  • the non-exposed portion of the composition layer can be removed by development using a developer.
  • a non-exposed portion of the composition layer in the exposure step is eluted into the developer, and only the photocured portion remains on the support.
  • the temperature of the developer is preferably 20°C to 30°C.
  • the development time is preferably 20 to 180 seconds.
  • a step of shaking the developer off per 60 seconds and supplying a new developer may be repeated multiple times.
  • the developer examples include an organic solvent and an alkali developer, and an alkali developer is preferably used.
  • an alkali developer an alkaline aqueous solution (alkali developer) in which an alkaline agent is diluted with pure water is preferable.
  • alkaline agent examples include: organic alkaline compounds such as ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxyamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, ethyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethyl bis(2-hydroxyethyl)ammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo[5.4.0]-7-undecene; and inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium silicate, and sodium metasilicate.
  • organic alkaline compounds such as ammonia, ethylamine, diethyl
  • the alkaline agent is preferably a compound having a high molecular weight.
  • a concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001 to 10 mass% and more preferably 0.01 to 1 mass%.
  • the developer may further contain a surfactant. Examples of the surfactant include the surfactants described above. Among these, a nonionic surfactant is preferable. From the viewpoint of easiness of transport, storage, and the like, the developer may be obtained by temporarily preparing a concentrated solution and diluting the concentrated solution to a necessary concentration during use.
  • the dilution factor is not particularly limited and, for example, can be set to be in a range of 1.5 to 100 times.
  • the layer is washed (rinsed) with pure water after development.
  • the rinsing is performed by supplying a rinsing liquid to the composition layer after development while rotating the support on which the composition layer after development is formed.
  • the rinsing is performed by moving a nozzle discharging the rinsing liquid from a center of the support to a peripheral edge of the support. In this case, in the movement of the nozzle from the center of the support to the peripheral edge of the support, the nozzle may be moved while gradually decreasing the moving speed of the nozzle.
  • the additional exposure treatment or the post-baking is a curing treatment after development in order to complete curing.
  • the heating temperature in the post-baking is preferably, for example, 100°C to 260°C.
  • the lower limit of the heating temperature is preferably 120°C or higher and more preferably 160°C or higher.
  • the upper limit of the heating temperature is preferably 240°C or lower and more preferably 220°C or lower.
  • the film after development is post-baked continuously or batchwise using a heating unit such as a hot plate, a convection oven (hot air circulation dryer), and a high-frequency heater under the above-described conditions.
  • light used for the exposure is preferably light having a wavelength of 400 nm or less.
  • the additional exposure treatment may be carried out by the method described in KR10-2017-0122130A .
  • the formation of a pattern using a dry etching method can be performed using a method including: applying the composition according to the embodiment of the present invention to a support to form a composition layer; curing the composition layer to form a cured composition layer; forming a patterned resist layer on the cured composition layer; and dry-etching the cured composition layer with etching gas by using the patterned resist layer as a mask.
  • the details of the pattern formation using the dry etching method can be found in paragraphs "0010" to "0067" of JP2013-064993A , the content of which is incorporated herein by reference.
  • An optical sensor according to the embodiment of the present invention includes the film according to the embodiment of the present invention.
  • Examples of the type of the optical sensor include an ambient light sensor and an illuminance sensor, and the optical sensor is preferably used as an ambient light sensor.
  • the ambient light sensor is a sensor which detects hue of ambient light.
  • the optical sensor according to the embodiment of the present invention has an optical filter having at least one pixel selected from a colored pixel or a pixel of an infrared transmitting filter, in addition to the film according to the embodiment of the present invention.
  • the colored pixel include a red pixel, a blue pixel, a green pixel, a yellow pixel, a cyan pixel, and a magenta pixel.
  • the film according to the embodiment of the present invention is provided closer to a light incident side than the above-described optical filter. By providing the film according to the embodiment of the present invention closer to the light incident side than the optical filter, angle dependence can be further reduced for each pixel.
  • An embodiment of the optical sensor is shown with reference to the drawings.
  • An optical sensor 1 shown in Fig. 1 is provided with an optical filter 110 having pixels 111 to 114 on a photoelectric conversion element 101.
  • a film 121 according to the embodiment of the present invention is formed on the optical filter 110.
  • the pixels 111 to 114 constituting the optical filter 110 a combination in which the pixel 111 is a red pixel, the pixel 112 is a blue pixel, the pixel 113 is a green pixel, and the pixel 114 is a pixel of an infrared transmitting filter can be mentioned.
  • the optical filter 110 having four types of pixels (pixels 111 to 114) is used, but the types of pixels may be one to three types or may be five or more types. The types can be appropriately selected according to the application.
  • a planarizing layer may be interposed between the photoelectric conversion element 101 and the optical filter 110, or between the optical filter 110 and the film 121 according to the embodiment of the present invention.
  • Fig. 2 shows another embodiment of the optical sensor.
  • An optical sensor 2 shown in Fig. 2 is provided with an optical filter 110 having pixels 111 to 114 on a photoelectric conversion element 101.
  • the optical filter 110 has the same configuration as that of the above-described embodiment.
  • a member in which a film 122 according to the embodiment of the present invention is formed on a surface of a transparent support 130 is disposed on the optical filter 110.
  • Examples of the transparent support 130 include a glass substrate and a resin substrate.
  • the member in which the film 122 according to the embodiment of the present invention is formed on the surface of the transparent support 130 is disposed on the optical filter 110 at predetermined intervals, but the optical filter 110 and the member in which the film 122 according to the embodiment of the present invention is formed on the surface of the transparent support 130 may be in contact with each other.
  • the film 122 according to the embodiment of the present invention is formed on only one surface of the transparent support 130, but the film 122 according to the embodiment of the present invention may be formed on both surfaces of the transparent support 130.
  • the film 122 according to the embodiment of the present invention is formed on the surface of the transparent support 130 on the optical filter 110 side, but the film 122 according to the embodiment of the present invention may be formed on the surface of the transparent support 130 opposite to the optical filter 110 side.
  • a planarizing layer may be interposed between the photoelectric conversion element 101 and the optical filter 110, or between the film 122 according to the embodiment of the present invention and the transparent support 130.
  • the primary particle diameter of the particles was obtained by observing particles with a transmission electron microscope (TEM) and observing a portion (primary particle) where the particles did not aggregate. Specifically, a particle size distribution was obtained by photographing a transmission electron micrograph of primary particles using a transmission microscope and measuring a particle size distribution with an image processing device using the micrograph.
  • the average primary particle diameter of the particles refers to the number average particle size calculated from the particle size distribution.
  • An electron microscope H-7000, manufactured by Hitachi, Ltd.
  • a LUZEX AP manufactured by Nireco Corporation
  • a dispersion liquid was prepared using the particles, a resin (dispersant) having a known refractive index, and propylene glycol monomethyl ether acetate.
  • the prepared dispersion liquid and a resin having a known refractive index were mixed with each other to prepare coating liquids in which the concentrations of the particles in the total solid content of the coating liquids was 10 mass%, 20 mass%, 30 mass%, and 40 mass%.
  • a film having a thickness of 300 nm was formed on a silicon wafer, and the refractive index of the obtained film was measured by ellipsometry (LAMBDA ACE RE-3300, manufactured by SCREEN Holdings Co., Ltd.).
  • the concentration and refractive index of the particles were plotted on a graph to calculate the refractive index of the particles.
  • a crystallization temperature (Tc) of a polymer was calculated by DSC measurement under the following measurement conditions.
  • the crystallization temperature of the polymer was measured as a crystallization temperature of a macromonomer used in the synthesis of each resin.
  • Approximately 5 mg of a polymer (macromonomer) to be measured was weighed, set in an aluminum pan for measurement, and attached to a differential scanning calorimeter (DSC, Q1000 type) manufactured by TA Instruments Japan. The measurement was carried out by raising the temperature from 25°C to 150°C at a rate of 10 °C/min, holding at 150°C for 5 minutes, and then cooling from 150°C to -30°C at a rate of 10 °C/min.
  • the crystallization temperature was defined as a peak top temperature of an exothermic peak appearing on a DSC curve obtained by the above-described method.
  • Tables 1 and 2 a case where the exothermic peak indicating the crystallization was not observed by the above-described method was described as "-”, and a case where the crystallization temperature exceeded 50°C was described as "> 50".
  • a weight-average molecular weight of the resin was measured by gel permeation chromatography (GPC) using the following conditions.
  • the acid value indicates the mass of potassium hydroxide required to neutralize an acidic component per 1 g of solid content.
  • a measurement sample was dissolved in a mixed solvent including tetrahydrofuran and water at a ratio (tetrahydrofuran/water) of 9/1, and the obtained solution was neutralized and titrated with a 0.1 mol/L sodium hydroxide aqueous solution at 25°C using a potentiometric titrator (trade name: AT-510, manufactured by Kyoto Electronics Manufacturing Co., Ltd.).
  • An inflection point of a titration pH curve was set as a titration end point, and the acid value was calculated from the following expression.
  • A 56.11 ⁇ Vs ⁇ 0.5 ⁇ f / w
  • a value according to the Okitsu method was used as the value of the solubility parameter (SP value).
  • SP value solubility parameter
  • documents describing the Okitsu method Toshinao Okitsu, The Journal of The Adhesion Society of Japan, vol. 29, No. 5, 204-211 (1993 ) or SP Value, Fundamentals-Applications and Calculation Method (Yamamoto, JOHOKIKO, CO., LTD., 2005) was referred to.
  • ⁇ -caprolactone (319.1 g), ⁇ -valerolactone (35.5), and 2-ethyl-1-hexanol (20.5 g) were charged into a three-neck flask, and the mixture was stirred while blowing nitrogen. Next, monobutyltin oxide (0.18 g) was added to the mixture, and the obtained mixture was heated to 90°C. After 7 hours, it was confirmed by 1 H-nuclear magnetic resonance (NMR) that a signal derived from 2-ethyl-1-hexanol which is a raw material in the mixture had disappeared, and then the mixture was heated to 110°C.
  • NMR 1 H-nuclear magnetic resonance
  • a polymerization reaction was continued at 110°C for 12 hours under nitrogen, then disappearance of signals derived from ⁇ -caprolactone and ⁇ -valerolactone was confirmed by 1 H-NMR, and the temperature of the mixture was lowered to 80°C.
  • a structure (Formula (MM-1)) of the macromonomer MM-1 was confirmed by 1 H-NMR.
  • a ratio of the constitutional unit L1 and the constitutional unit L2 was 90/10 (mass ratio) calculated from the charged weights of the ⁇ -caprolactone and ⁇ -valerolactone as raw materials.
  • the number of repetitions (value of p1 + p2 in Formula (MM-1)) was 20 calculated from the number of moles of the ⁇ -caprolactone, ⁇ -valerolactone, and 2-ethyl-1-hexanol as raw materials.
  • the repeating units are not limited to being linked in the order shown in the following structural formula to form a block for each repeating unit, and each repeating unit may be randomly linked.
  • the weight-average molecular weight of the macromonomer MM-1 was 6,000, and the crystallization temperature thereof was 6°C.
  • Macromonomers MM-2 to 14 were obtained by the same procedure as in Synthesis Example 1 (method for synthesizing the macromonomer MM-1), except that the type of lactone compound ( ⁇ -caprolactone and ⁇ -valerolactone) used in the synthesis of the macromonomer MM-1 and the charged amount thereof were changed as shown in Tables 1 and 2 so that the weight-average molecular weight and the number of repetitions were adjusted to desired values.
  • Structure (Formulae (MM-2) to (MM-14)) of the macromonomers MM-2 to MM-14 were confirmed by 1 H-NMR.
  • Tables 1 and 2 show the ratio of the constitutional unit L1 and the constitutional unit L2, the number of repetitions, the weight-average molecular weight, and the crystallization temperature of each macromonomer.
  • a macromonomers MM-15 was obtained by the same procedure as in Synthesis Example 6 (method for synthesizing the macromonomer MM-6), except that Karenz MOI (manufactured by SHOWA DENKO K.K., 2-isocyanatoethyl methacrylate) used in the synthesis of the macromonomer MM-6 was changed to Karenz AOI (manufactured by SHOWA DENKO K.K., 2-isocyanatoethyl acrylate) with the same number of moles.
  • a structure (Formula (MM-15)) of the macromonomer MM-15 was confirmed by 1 H-NMR. Table 2 shows the ratio of the constitutional unit L1 and the constitutional unit L2, the number of repetitions, the weight-average molecular weight, and the crystallization temperature.
  • PGMEA (120.2 g) was charged into a three-neck flask, and heated to 75°C while blowing nitrogen. Next, a mixed solution of ethyl methacrylate (109.6 g), methyl methacrylate (32.1 g), 6-mercapto-1-hexanol (8.34 g), 2,2'-azobis(2-methylpropionate) (V-601, manufactured by FUJIFILM Wako Pure Chemical Corporation) (0.81 g), and PGMEA (98.3 g) was added dropwise to the solution in the flask over 2 hours under a nitrogen atmosphere, and the mixture was stirred at 75°C for 1 hour.
  • ethyl methacrylate 109.6 g
  • methyl methacrylate 32.1 g
  • 6-mercapto-1-hexanol 8.34 g
  • 2,2'-azobis(2-methylpropionate) V-601, manufactured by FUJIFILM Wako Pure Chemical Corporation
  • PGMEA
  • V-601 (0.81 g) was added to the mixture, and the mixture was further stirred at 75°C for 2 hours.
  • V-601 (0.81 g) was added to the mixture, the mixture was further stirred at 90°C for 3 hours, and the mixture was cooled to 0°C.
  • a structure (Formula (MM-91)) of the macromonomer MM-91 was confirmed by 1 H-NMR.
  • a ratio of p1 and p2 in Formula (MM-91) was 77/23 (mass ratio) calculated from the charged weights of the ethyl methacrylate and methyl methacrylate as raw materials.
  • the number of repetitions (value of p1 + p2 in Formula (MM-91)) was 21 calculated from the number of moles of the ethyl methacrylate, methyl methacrylate, and 6-mercapto-1-hexanol as raw materials.
  • the repeating units are not limited to being linked in the order shown in the following structural formula to form a block for each repeating unit, and each repeating unit may be randomly linked.
  • the weight-average molecular weight of the macromonomer MM-91 was 4,100, and no exothermic peak indicating the crystallization was not observed.
  • the macromonomer MM-1 solution (PGMEA: 50 mass%, 60.0 g; 50 mass% with respect to the total mass of all monomers), NK ESTER CB-1 as a monomer for obtaining the constitutional unit B (manufactured by Shin-Nakamura Chemical Co., Ltd., mono-2-(methacryloyloxy)ethyl phthalate) (18.0 g, 30 mass% with respect to the total mass of all monomers), benzyl methacrylate as a monomer for obtaining the constitutional unit C (12.0 g, 20 mass% with respect to the total mass of all monomers), and PGMEA (81.4 g) were charged into a three-neck flask, and the mixture was stirred while blowing nitrogen and heated to 75°C.
  • 1-dodecanethiol as a chain transfer agent (0.88 g, 3 mol% with respect to the total number of moles of all monomers) and then V-601 as a polymerization initiator (0.22 g, 22 mol% with respect to the total number of moles of all monomers) were added to the mixture to initiate a polymerization reaction.
  • V-601 (0.22 g) was further added to the mixture.
  • V-601 (0.22 g) was further added to the mixture.
  • the formula weight of the constitutional unit A in the resin A-1 was 1,000 or more.
  • Resins A-2 to A-36, A-101, and B-1 to B-3 (compounds having structures represented by Formulae (A-2) to (A-36), (A-101), and (B-1) to (B-3)) were obtained by the same procedure as in Synthesis Example 16 (method for synthesizing the resin A-1), except that the type of the macromonomer, the type of the monomer for obtaining the constitutional unit B, the type of the monomer for obtaining the constitutional unit C, the charged amounts thereof, and the charged amount of the chain transfer agent used in the synthesis of the resin A-1 were changed as shown in Tables 1 and 2.
  • Tables 1 and 2 show the weight-average molecular weight, the acid value, and the SP value of each resin.
  • the formula weights of the constitutional unit A in the resins A-2 to A-36 and A-101 was all 1,000 or more.
  • [Table 1] Resin name Constitutional unit A Constitutional unit B Constitutional unit C Chain transfer agent amount (mol%) Weight-average molecular weight Acid value (mgKOH/g) SP value (MPa 0.5 ) Raw material macromonomer Compositional ratio (mass%) Raw material monomer name Compositional ratio (mass%) Raw material monomer name Compositional ratio (mass%) Name Constitutional unit L1 Constitutional unit L2 or constitutional unit L3 Number of repetitions Weight-average molecular weight Crystallization temperature (°C) Type Compositional ratio (mass%) Type Compositional ratio (mass%) A-1 MM-1 L-1 90 L-2 10 20 6000 6 50 MB-1 30 MC-1 20 3 27300 59 20.22 A-2 MM-2 L-1 85 L-2 15 20 6000 -1 50 MB-1 30 MC-1 20 3 27500 58 20.24 A-3 MM-3 L-1 70 L-2 30 20 5
  • L-1 to L-3, L-11, L-12, L-13 structures shown below
  • Itaconic acid (261.7 g), dipentaerythritol hexakis(3-mercaptopropionate) (DPMP) (450.0 g), and propylene glycol monomethyl ether (PGME) (1,661 g) were added to a three-neck flask, and the mixture was stirred and heated to 80°C under a nitrogen atmosphere. Next, V-601 (1.16 g) was added thereto and stirred for 2 hours.
  • DPMP dipentaerythritol hexakis(3-mercaptopropionate)
  • PGME propylene glycol monomethyl ether
  • V-601 (1.16 g) was added thereto, and the mixture was heated to 90°C and stirred for 2 hours to obtain a 30 mass% solution (2375 g) of a modified thiol X-1 (compound in which an average of 3.5 of 6 thiols in one molecule of DPMP was modified with itaconic acid).
  • PGMEA (64.1 g) was added to a three-neck flask, and heated to 80°C under a nitrogen atmosphere. Next, a mixed solution of the modified thiol X-1 (104.5 g), methyl methacrylate (88.7 g), V-601 (0.61 g, 0.3 mol% of methyl methacrylate), and PGMEA (15.2 g) was added dropwise to the solution in the flask over 2.5 hours. After completion of the dropwise addition, the mixture was stirred for 2.5 hours, and V-601 (0.61 g) was added thereto.
  • the mixture was heated to 90°C and stirred for 2 hours, and PGMEA (127.2 g) was added thereto to obtain a 30 mass% solution of a resin B-101 (compound having a structure represented by Formula (B-101)).
  • the weight-average molecular weight of the obtained resin B-101 was 6,300, the acid value thereof was 83 mgKOH/mg, and the SP value thereof was 20.53 MPa 0.5 .
  • PGMEA (108.3 g) was added to a three-neck flask, and heated to 80°C under a nitrogen atmosphere. Next, a mixed solution of the modified thiol X-1 (117.3 g), methyl methacrylate (147.1 g), methacrylic acid (12.1 g), V-601 (1.11 g, 0.3 mol% with respect to the total number of moles of all monomers), and PGMEA (170.6 g) was added dropwise to the solution in the flask over 2.5 hours. After completion of the dropwise addition, the mixture was stirred for 2.5 hours, and V-601 (1.11 g) was added thereto.
  • a ratio of q1 and q2 in Formula (B-102) was 92.4/7.6 (mass ratio) calculated from the charged weights of the methyl methacrylate and methacrylic acid as raw materials.
  • the number of repetitions (value of q1 + q2 in Formula (B-102)) was 22.7 calculated from the number of moles of the modified thiol, methyl methacrylate, and methacrylic acid as raw materials.
  • the repeating units are not limited to being linked in the order shown in the following structural formula to form a block for each repeating unit, and each repeating unit may be randomly linked.
  • the weight-average molecular weight of the obtained resin B-102 was 9,200, the acid value thereof was 100 mgKOH/mg, and the SP value thereof was 20.43 MPa 0.5 .
  • Resins B-103 to B-109 were obtained by the same procedure as in Synthesis Example 58 (method for synthesizing the resin B-102), except that the charged amount of the monomer (methyl methacrylate and methacrylic acid) used in the synthesis of the resin B-102 was adjusted so that the compositional ratio and the number of repetitions were as shown in Table 3.
  • Table 3 shows the compositional ratio, the number of repetitions, the weight-average molecular weight, the acid value, and the SP value of each resin.
  • PGMEA (20.3 g) was added to a three-neck flask, and heated to 80°C under a nitrogen atmosphere.
  • a mixed solution of the modified thiol X-1 (117.3 g), the 50 mass% PGMEA solution (197.3 g) of the macromonomer MM-15, V-601 (0.049 g, 0.3 mol% with respect to the number of moles of all monomers), and PGMEA (47.5 g) was added dropwise to the solution in the flask over 2.5 hours. After completion of the dropwise addition, the mixture was stirred for 2.5 hours, and V-601 (0.049 g) was added thereto.
  • the mixture was heated to 90°C and stirred for 2 hours, and PGMEA (63.7 g) was added thereto to obtain a 30 mass% solution of a resin A-102 (compound having a structure represented by Formula (A-102)).
  • the weight-average molecular weight of the obtained resin A-102 was 9,700, the acid value thereof was 83 mgKOH/mg, and the SP value thereof was 20.84 MPa 0.5 .
  • the formula weight of the constitutional unit A in the resin A-102 was 1,000 or more.
  • Resin name Compositional ratio (mass%) Number of repetitions Weight-average molecular weight Acid value (mgKOH/g) SP value (MPa 0.5 ) q1 q2 B-101 100 - 14 6300 83 20.53 B-102 92.4 7.6 22.7 9200 100 20.43 B-103 88.7 11.3 22.7 9200 118 20.55 B-104 85.0 15.0 22.7 9300 135 20.68 B-105 81.3 18.7 22.7 9400 157 20.80 B-106 77.5 22.5 22.7 9500 181 20.93 B-107 88.1 11.9 14.9 6700 141 20.84 B-108 83.4 16.6 30.6 12000 141 20.58 B-109 82.5 17.5 38.4 14400 139 20.52 A-102 85 15 10 9700 83 20.84
  • the value of the refractive index in the above tables is a refractive index for light having a wavelength of 589 nm.
  • Dispersion liquid Resin (binder) Polymerizable monomer Photosensitive initiator Additive Surfactant Polymerization inhibitor Solvent Type Part by mass Type Part by mass Type Part by mass Type Part by mass Type Part by mass Type Part by mass Type Part by mass Type Part by mass Type Part by mass Example 1
  • Example 5 Dispersion liquid 4 52 A-2 8.96 M-2 9.58
  • Dispersion Liquids 1 to 21 dispersion liquids 1 to 21 described above
  • the coating film was heat-treated (pre-baked) using a hot plate at 110°C for 30 minutes.
  • an i-ray stepper exposure device FPA-3000 i5+ manufactured by Canon Corporation
  • the coating film was exposed to light having a wavelength of 365 nm at an exposure amount of 1000 mJ/cm 2 .
  • a heating treatment post-baking was performed for 5 minutes used a hot plate at 200°C to form a film.
  • the light transmittance of the obtained film in a wavelength in a range of 400 to 1,000 nm was measured, and a difference in transmittance between 450 nm and 940 nm was measured.
  • the transmittance difference ⁇ T% was evaluated according to the following standard. The evaluation results are described in the column of "Light scattering properties" of tables described later.
  • the coating film was exposed to light having a wavelength of 365 nm at an exposure amount of 1,000 mJ/cm 2 . Thereafter, a heating treatment (post-baking) was performed for 5 minutes used a hot plate at 200°C to form a film.
  • the maximum value (T1) of the transmittance of the film formed of the 1 cm solution from the top at a wavelength of 400 to 1,000 nm, the maximum value (T2) of the transmittance of the film formed of the 1 cm solution from the bottom at a wavelength of 400 to 1,000 nm, and ⁇ T which is the difference (T1 - T2) were determined, and storage stability was evaluated according to the following evaluation standard. As ⁇ T is smaller, the storage stability is better. The evaluation results are described in the column of "Storage stability" of tables described later.
  • Each composition was applied to a silicon substrate using a spin coater (manufactured by Mikasa Co., Ltd.) such that the film thickness after post-baking was 4 ⁇ m. As a result, a coating film was formed.
  • a hot plate heating (pre-baking) was performed at 100°C for 120 seconds, and then the mixture was allowed to stand for 72 hours.
  • an i-ray stepper exposure device FPA-3000 i5+ manufactured by Canon Corporation
  • heating (post-baking) was performed again at 200°C for 300 seconds using a hot plate to obtain a film.
  • the generation of foreign matter over time was evaluated according to the following evaluation standard. As the number of foreign matters is smaller, the generation of the foreign matter over time is more suppressed. The evaluation results are described in the column of "Foreign matter over time" of tables described later.
  • the coating film was heat-treated (pre-baked) using a hot plate at 110°C for 120 minutes.
  • the coating film was exposed to light having a wavelength of 365 nm (exposure amount: 50 to 1,700 mJ/cm 2 ) through a pattern mask which forms 25 lines with a width of 100 ⁇ m and a length of 1,000 ⁇ m.
  • composition layer after exposure was developed using a developing device (Act8 manufactured by Tokyo Electron Limited.).
  • shower development was performed at 23°C for 60 seconds using, as a developer, a tetramethylammonium hydroxide (TMAH) 0.3 mass% aqueous solution.
  • TMAH tetramethylammonium hydroxide
  • the resultant was rinsed by a spin shower using pure water, spin-dried, and then heat-treated (post-baked) for 5 minutes using a hot plate at 200°C to obtain a pattern.
  • the difference ⁇ E (E2 - E1) between the minimum exposure amount E1 required to form the pattern with a width of 100 ⁇ m and a length of 1,000 ⁇ m and the minimum exposure amount E2 required for all the patterns to adhere is obtained, and adhesiveness was evaluated according to the following evaluation standard. The evaluation results are described in the column of "Adhesiveness" of tables described later. As ⁇ E is smaller, the adhesiveness is better. The close adhesion of the patterns and the size of the patterns were observed using an optical microscope (magnification: 200 times).
  • the coating film was heat-treated (pre-baked) using a hot plate at 110°C for 30 minutes.
  • FPA-3000 i5+ manufactured by Canon Corporation
  • the coating film was exposed to light having a wavelength of 365 nm at an exposure amount of 1,000 mJ/cm 2 .
  • a heating treatment post-baking
  • the transmittance of the obtained film to light having a wavelength in a range of 400 to 1,000 nm was measured, and the maximum value of the transmittance in the range was measured.
  • the maximum value of the transmittance was evaluated based on the following standard. The evaluation results are described in the column of "Maximum value of transmittance" of tables described later.
  • the coating film was heat-treated (pre-baked) using a hot plate at 110°C for 30 minutes.
  • an i-ray stepper exposure device FPA-3000 i5+ manufactured by Canon Corporation
  • the coating film was exposed to light having a wavelength of 365 nm at an exposure amount of 1,000 mJ/cm 2 .
  • a heating treatment post-baking was performed for 5 minutes used a hot plate at 200°C to form a film.
  • the difference between the SP value of the resin in the dispersion liquid used as a dispersant and the SP value of the resin in the composition used as a binder is described in the column of "Difference in SP value between dispersant and binder (MPa 1/2 )" of tables.
  • composition according to Examples is excellent in storage stability, and the film obtained by the composition according to Examples is excellent in light scattering properties and adhesiveness.
  • the evaluation of the light scattering properties, the evaluation of the storage stability, the measurement of the maximum value of the transmittance, and the confirmation of the phase separation state were performed by the same methods as described above, except that, in the evaluation of the light scattering properties, the evaluation of the storage stability, the measurement of the maximum value of the transmittance, and the confirmation of the phase separation state, the operation of "applied using a spin coater such that the thickness after post-baking was 4 ⁇ m" was changed to "applied using a spin coater such that the thickness after post-baking was 8 ⁇ m". All the evaluation results were the same as the evaluation results in the case of 4 ⁇ m.
  • the evaluation of the adhesiveness and the evaluation of the foreign matter over time were performed by the same methods as described above, except that, in the evaluation of the adhesiveness and the evaluation of the foreign matter over time, the operation of "such that the film thickness after pre-baking was 4 ⁇ m" was changed to "such that the film thickness after pre-baking was 4 ⁇ m". All the evaluation results were the same as the evaluation results in the case of 4 ⁇ m.
  • the optical sensor described in Fig. 1 of Reference A was produced with reference to the description of Reference A, except that a diffuser 10 was changed to the film composed of the composition prepared in any of Examples 1 to 78 described above.
  • the obtained optical sensor operated normally in any case of the composition prepared in any of Examples 1 to 78.
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